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Publication Date: 2026
Journal of Molecular Structure (00222860) 1350
Structural studies of five pyrazolo[3,4-b]-4,9-dihydroquinoline-5-one and pyrazolo[3,4-b]quinoline-5-one derivatives were performed by analyzing their single crystal structures. X-ray crystallographic analysis of two pyrazolo[3,4-b]-4,9-dihydroquinoline-5-ones successfully addressed the challenges raised regarding the occurrence of possible tautomeric forms for structures without substitution on the N1-atom of the pyrazole ring. Furthermore, DFT computational studies confirmed and strengthened these results by comparison of the total energy content of both tautomeric forms. Results of both studies revealed the definitive presence of more stable N2-H pyrazole ring in these structures. Single crystal structure studies and Hirshfeld surfaces analysis clearly demonstrated the occurrence of the intermolecular interactions (hydrogen bonding and π-π stacking), which are essential for investigation of the crystal stability and cohesion. DFT computational studies on the optimized structures of the target molecules by comparing characteristic bond lengths, NBO atomic charges, and molecular electrostatic potential (MEP) mapping indicated the change in the electron density and its effect on establishment of intermolecular interactions. The energies of frontier molecular orbitals (FMOs) also lead to understanding the global reactivity descriptors (GRDs) in each molecule. © 2025
Publication Date: 2025
Medicinal Research Reviews (01986325) 45(2)pp. 654-754
Chirality is a fundamental and widespread geometric structural property in living organisms that most biomacromolecules including nucleic acids, proteins and enzymes, possess. Consequently, the development of chiral drugs capable of binding specific targets have gradually gained wide attention in recent decades due to their selective effects on a broad spectrum of biological events ranging from cell metabolism to cell fate. In this context, the synthesis of chiral compounds as promising therapeutic candidates has assumed a major role in drug discovery. Among them, chiral metal complexes have attracted considerable interest due to their unique and intriguing structural features that could enable overcoming side effects and drug-resistance phenomena of metal−based drugs currently in the market such as cisplatin. In the current scenario, an in-depth overview of non-platinum chiral complexes needs to be presented and carried forward. Therefore, in this perspective article, an update of the scientific development of bioactive chiral copper, zinc and nickel complexes have been reported since they have not been thoroughly reviewed so far. Specifically, we focused the article mainly on metal complexes containing chiral ligands (type 2 chirality) as in literature they are more numerous than those with chirality at the metal center (type 1 chirality). Herein, not only their biological activity but also their mechanism of action is summarized. Furthermore, in the final section of the article we have highlighted copper-based complexes as those with a superior biological activity profile and greater prospects for development as a drug. © 2024 Wiley Periodicals LLC.
Publication Date: 2025
Applied Organometallic Chemistry (02682605) 39(6)
A samarium-based metal–organic framework (MOF) containing benzophenone-4,4′-dicarboxylate (bpndc) linker was synthesized and characterized using X-ray crystallography and spectroscopy methods. The crystal structure analysis revealed that the MOF is a three-dimensional 3-nodal 5-c net. The prepared MOF was used as a catalyst in glycerol acetalization to produce solketal as a fuel additive. The catalyst with suitable thermal stability and acidic characteristics resulted in 93.7% glycerol conversion with solketal selectivity of 90.1%. This study further supports the effectiveness of Ln-based MOF as potential Lewis acid catalysts for chemical transformations. © 2025 John Wiley & Sons Ltd.
Publication Date: 2025
Journal of Molecular Structure (00222860) 1330
The conformational analysis of three 3,5-disubstituted 4,5-dihydro-1,2,4-oxadiazoles (DHOZs) was investigated using X-ray crystal structure and DFT computations. Mechanistically, nucleophilic attack of either the hydroxy or the amino group of the amidoxime precursor to the re- or si-faces of the aldehyde carbonyl group and the following intramolecular cyclization results normally in the formation of the R/S-enantiomeric pair with the stereocenter on the C5-atom of the heterocyclic ring. Surprisingly, the crystal packing of the investigated compounds revealed the presence of the pure R-enantiomer, pure S-enantiomer, and the racemic mixture. The optical activities of the molecules are confirmed by recording their CD spectra. Crystal packing is explored based on the acting intra- and intermolecular interactions using the quantum theory of atoms-in-molecules (QTAIM), noncovalent interaction plot (NCI plot), reduced density gradient (RDS), Hirshfeld surface (HS) analysis, and two-dimensional fingerprint (2D-FP) plots. The computational structural characteristics of the optimized geometries of the considered DHOZs are compatible with those in the crystal packing. Furthermore, the computational conformational analysis of the imino-oxime intermediate, involved in the intramolecular cyclization process, support the experimental findings. © 2025
Publication Date: 2024
Journal Of The Iranian Chemical Society (1735207X) 21(7)pp. 1997-2015
Crystal structure analysis and DFT computational calculation of two symmetrical and unsymmetrical decahydroacridine-1,8-diones (DHACs) were carried out to elucidate the effect of the aryl-substituted heterocyclic core in these compounds on the comparative bond lengths, bond, and dihedral angles. According to these findings, the central heterocyclic ring in these compounds is exhibited in the pseudo-boat conformation, in which the aryl substitution occupies the pseudo-axial position. Moreover, the fused outer rings were in the twisted half-chair conformation. The weak and strong inter- and intramolecular interactions between the suitable donor–acceptor positions (N‒H···O, C‒H···O, H‒N···H and C‒H···π of the C=C double bond) in symmetrical and enantiomeric pairs of unsymmetrical DHACs affect the orientation of the molecules in the crystal packing. The relative contributions of various intermolecular interactions in these compounds are evaluated using Hirshfeld surface analysis. The DFT calculations were performed to outline the optimized structure, molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs), natural bond orbital (NBO) and to elucidate the effect of the space orientation of the attached aryl ring toward the heterocyclic ring on the total energy content of DHAC 2. Additionally, MEP analysis in DHAC 2 revealed that the negative electrostatic potential is more concentrated around the O1-atom of the C1=O1 double bond than the O2-atom of the C13=O2 double bond. The results of the NBO analysis demonstrated that in the crystal packing of compounds 1 and 2 the strongest intermolecular interaction occurs from the LP(2)O2 to σ*(N1–H) and LP(1)O1 to σ*(N1‒H), respectively. © Iranian Chemical Society 2024.
Kazemi, Z. ,
Amiri rudbari, H. ,
Moini, N. ,
Momenbek, F. ,
Carnamucio, F. ,
Micale, N. Publication Date: 2024
Molecules (14203049) 29(2)
Indole is an important element of many natural and synthetic molecules with significant biological activity. Nonetheless, the co-presence of transitional metals in organic scaffold may represent an important factor in the development of effective medicinal agents. This review covers some of the latest and most relevant achievements in the biological and pharmacological activity of important indole-containing metal complexes in the area of drug discovery. © 2024 by the authors.
Taghizadeh shool, M. ,
Amiri rudbari, H. ,
Cuevas-vicario, J.V. ,
Rodríguez-rubio, A. ,
Stagno, C. ,
Iraci, N. ,
Efferth, T. ,
Omer, E.A. ,
Schirmeister, T. ,
Blacque, O. Publication Date: 2024
Inorganic Chemistry (00201669) 63(2)pp. 1083-1101
A novel class of Ru(II)-based polypyridyl complexes with an auxiliary salicylaldehyde ligand [Ru(phen)2(X-Sal)]BF4 {X: H (1), 5-Cl (2), 5-Br (3), 3,5-Cl2 (4), 3,5-Br2 (5), 3-Br,5-Cl (6), 3,5-I2 (7), 5-NO2 (8), 5-Me (9), 4-Me (10), 4-OMe (11), and 4-DEA (12), has been synthesized and characterized by elemental analysis, FT-IR, and 1H/13C NMR spectroscopy. The molecular structure of 4, 6, 9, 10, and 11 was determined by single-crystal X-ray diffraction analysis which revealed structural similarities. DFT and TD-DFT calculations showed that they also possess similar electronic structures. Absorption/emission spectra were recorded for 2, 3, 10, and 11. All Ru-complexes, unlike the pure ligands and the complex lacking the salicylaldehyde component, displayed outstanding antiproliferative activity in the screening test (10 μM) against CCRF-CEM leukemia cells underlining the crucial role of the presence of the auxiliary ligand for the biological activity. The two most active derivatives, namely 7 and 10, were selected for continuous assays showing IC50 values in the submicromolar and micromolar range against drug-sensitive CCRF-CEM and multidrug-resistant CEM/ADR5000 leukemia cells, respectively. These two compounds were investigated in silico for their potential binding to duplex DNA well-matched and mismatched base pairs, since they showed remarkable selectivity indexes (2.2 and 19.5 respectively) on PBMC cells. © 2023 American Chemical Society.
Publication Date: 2024
Journal of Photochemistry and Photobiology A: Chemistry (18732666) 449
Various 2,4-bisaryl substituted 5-oxohexahydroquinolines were synthesized and the electronic effects of 2- and 4-substitutions on the photochemical behaviors of these compounds were investigated. UV light irradiation of these compounds resulted in the occurrence of two types of photoreactions; oxidative normal photo-oxidation and photo-rearranged reactions. In both reactions, the aromatization of the heterocyclic 1,4-dihydropyridine ring to the pyridine ring was observed. The photochemical results indicated the involvement of the radical intermediate, responsible for the aryl ring migration and the occurrence of the photo-rearrangement reaction. The partial synergistic effect of the capto-dative radical stabilization of the involved radical intermediate was supported by the results of the experimental works and the DFT-computational studies. X-ray crystal structure analysis of two of 5-oxohexahydroquinoline compounds indicated that i). The C4-aryl ring occupies the pseudo-axial position of the twisted-boat conformation of the heterocyclic dihydropyridine ring and, ii). Owing to the steric ortho-repulsion, the C2-aryl ring has a non-planar orientation concerning the attached C[dbnd6]C double bond of the heterocyclic ring. These observations were in good agreement with the data of the DFT-computational studies and the X-ray crystal structure analysis. © 2023 Elsevier B.V.
Forooghi, K. ,
Amiri rudbari, H. ,
Stagno, C. ,
Iraci, N. ,
Cuevas-vicario, J.V. ,
Kordestani, N. ,
Schirmeister, T. ,
Efferth, T. ,
Omer, E.A. ,
Moini, N. Publication Date: 2024
Dalton Transactions (14779226) 53(25)pp. 10571-10591
In order to investigate the structural features and antiproliferative activity of Pd(ii) complexes containing halogenated ligands with different flexibility, several Schiff base and reduced Schiff base Pd(ii) complexes, namely X1X2PicPd, X1X2PyPd, X1X2Pic(R)Pd, and X1X2Py(R)Pd (where X1 = X2 = Cl, Br and I; Pic: 2-picolylamine; Py = 2-(2-pyridyl)ethylamine), were synthesized and characterized by spectroscopic methods and, in the case of Br2PyPd, Cl2Py(R)Pd and ClBrPy(R)Pd, also by X-ray crystallography. The results of the X-ray crystallography showed that in both series of complexes the Pd(ii) ion has a distorted square-planar geometry, although the coordination modes of the two ligands are different. In the Schiff base-type complexes the ligand acts as a tridentate chelate with NN′O donor atoms, whereas in the reduced Schiff base-type complexes the ligand acts as a bidentate chelate with NN′ donor atoms. In both series of complexes, the chloride ions occupy the residual coordination sites of the Pd(ii) ion. TD-DFT calculations were performed for a better understanding of the UV-Vis spectra. From these calculations it was found that the signal appearing at ∼400 nm in the complexes with reduced Schiff base ligands (X1X2Pic(R)Pd and X1X2Py(R)Pd) is mainly due to a HOMO → LUMO transition, while for the Schiff base complex ClBrPyPd the signal is due to a HOMO → LUMO+1 transition. For the complex I2PicPd, combinations of HOMO−4 → LUMO and HOMO−2 → LUMO transitions were found to be responsible for that signal. In regard to the biological activity profile, all complexes were first investigated as proteasome inhibitors by fluorometric methods. From these enzymatic assays, it emerged that they are good inhibitors with IC50 values in the low-micromolar range and that their inhibitory activity is strictly related to the presence of the metal ion. Subsequently they were also subjected to cell-based assays (the resazurin method) to assess their antiproliferative properties by using two leukemic cell lines, namely the drug-sensitive CCRF-CEM cell line and its multidrug-resistant sub-cell line CEM/ADR5000. In this test they displayed IC50 values in the sub-micromolar and low-micromolar range determined for a selected metal complex (Br2Pic(R)Pd) and ligand (Cl2Pic(R)), respectively. Moreover, docking studies were performed on the two expected molecular targets, i.e. proteasome and DNA, to shed light on the mechanisms of action of these types of Pd(ii) complexes. © 2024 The Royal Society of Chemistry.
Aryaeifar, M. ,
Amiri rudbari, H. ,
Moreno-pineda, E. ,
Cuevas-vicario, J.V. ,
Paul, S. ,
Schulze, M. ,
Wernsdorfer, W. ,
Lloret, F. ,
Moini, N. ,
Blacque, O. Publication Date: 2024
New Journal of Chemistry (11440546) 48(8)pp. 3603-3613
Four Ni4O4 cubanes with formula [Ni4(Cl2-L)4(μ3-OMe)4(MeOH)4] (1), [Ni4(Br2-L)4(μ3-OMe)4(MeOH)4] (2), [Ni4(I2-L)4(μ3-OMe)4(MeOH)4] (3) and [Ni4(BrCl-L)4(μ3-OMe)4(MeOH)4] (4) (Cl2-LH = 3,5-dichlorosalicylaldehyde, Br2-LH = 3,5-dibromosalicylaldehyde, I2-LH = 3,5-diiodosalicylaldehyde, BrCl-LH = 3-bromo-5-chlorosalicylaldehyde) were obtained by self-assembly from commercially available 3,5-halogen-substituted salicylaldehydes and NiCl2·6H2O in high yields at room temperature. The X-ray crystal structure analysis of 4 showed a cubane-type structural topology as each Ni(ii) ion is six-coordinated in a distorted octahedral geometry defined by four oxygen atoms from the MeOH molecule (three as bridging methoxy-oxygens and one as terminal group) and two oxygen atoms from the 3-bromo-5-chlorosalicylaldehyde ligands. The cubane core is stabilized via an intramolecular O-H⋯O hydrogen bond, while in the crystal, complex molecules are linked into the zigzag chain to the a-axis via strong Br⋯Br interaction. Both SQUID and μSQUID measurements indicate the coexistence of ferromagnetic and antiferromagnetic interactions in two complexes. The fitting of the magnetic data yields different magnetic parameters for each complex, clearly highlighting the differences in the magnetic properties among these systems. DFT calculations have also been performed on compounds 1-4 to explain the exchange interaction mechanisms between the Ni(ii) ions, supporting both the magnitude and sign of the coupling constants. © 2024 The Royal Society of Chemistry.
Publication Date: 2024
19(72)pp. 283-304
Coordination polymers (CPs) are synthesized using bridging organic ligands and metal ions, depending on the geometric coordination of the metal, the bridging ligands, and the donor atoms present in these ligands, various one-, two-, or three-dimensional polymeric structures can form. To investigate the effect of the position of the pyridine nitrogen atom in the tridentate NN'O Schiff base ligand on the type of coordination polymers, two copper complexes were prepared. The ligand HL2 was characterized using IR, NMR, and elemental analysis, while the complexes were analyzed and identified using IR, elemental analysis, and X-ray diffraction techniques. The structural data of the copper complexes indicated that changing the pyridine nitrogen from position 3 to position 4 in the Schiff base ligand altered the structure of the copper complex from two-dimensional to three-dimensional. Analysis of inter-and intramolecular interactions using the NCI program shows that the interactions in both molecules are of the hydrogen bonding, halogen bonding, CH…π, π…π stacking, metal…π, and lone-pair…π type. © 2024 Semnan University.
Publication Date: 2023
Journal of Photochemistry and Photobiology A: Chemistry (18732666) 435
A series of 4-hydroxy- or 4-methoxy-substituted 1,3,5-triaryl-2-pyrazolines were synthesized and their structures, especially trans-orientation of 4- and 5-hydrogens of the 2-pyrazoline ring were characterized by analysis of IR, 1H NMR, 13C NMR spectra as well as the single-crystal structure study. In order to elucidate the effect of 4-hydroxy- or 4-methoxy-substitution on the photochemical behavior of these compounds, they were exposed to the UV light. The results explain the occurrence of a non-oxidative photoreaction, by the expulsion of 4-substitution and elimination of a molecule of water or methanol under the formation of the aromatized pyrazole ring. Density functional theory (DFT) calculations were carried out to support the proposed electron-transfer induced photoreaction mechanism. Natural bond orbital (NBO) analysis explains the preferred electron detachment process from the N1-atom rather than the oxygen atom of the hydroxy or the methoxy groups. Proton detachment from the involved radical cation species leads to the formation of the radical intermediate centered at the C5-position of the heterocyclic ring. Elimination of the hydroxy or the methoxy group accomplished the photoreaction under the formation of the C4-unsubstituted pyrazole molecule. © 2022 Elsevier B.V.
Zhou, M. ,
Boulos, J.C. ,
Omer, E.A. ,
Amiri rudbari, H. ,
Schirmeister, T. ,
Micale, N. ,
Efferth, T. Publication Date: 2023
European Journal of Pharmacology (00142999) 956
The use of cisplatin and its derivatives in cancer treatment triggered the interest in metal-containing complexes as potential novel anticancer agents. Palladium (II)-based complexes have been synthesized in recent years with promising antitumor activity. Previously, we described the synthesis and cytotoxicity of palladium (II) complexes containing halogen-substituted Schiff bases and 2-picolylamine. Here, we selected two palladium (II) complexes with double chlorine-substitution or double iodine-substitution that displayed the best cytotoxicity in drug-sensitive CCRF-CEM and multidrug-resistant CEM/ADR5000 leukemia cells for further biological investigation. Surprisingly, these compounds did not significantly induce apoptotic cell death. This study aims to reveal the major mode of cell death of these two palladium (II) complexes. We performed annexin V-FITC/PI staining and flow cytometric mitochondrial membrane potential measurement followed by western blotting, immunofluorescence microscopy, and alkaline single cell electrophoresis (comet assay). J4 and J6 still induced neither apoptosis nor necrosis in both leukemia cell lines. They also insufficiently induced autophagy as evidenced by Beclin and p62 detection in western blotting. Interestingly, J4 and J6 induced a novel mode of cell death (parthanatos) as mainly demonstrated in CCRF-CEM cells by hyper-activation of poly(ADP-ribose) polymerase 1 (PARP) and poly(ADP-ribose) (PAR) using western blotting, flow cytometric measurement of mitochondrial membrane potential collapse, nuclear translocation of apoptosis-inducing factor (AIF) by immunofluorescence microscopy, and DNA damage by alkaline single cell electrophoresis (comet assay). AIF translocation was also observed in CEM/ADR5000 cells. Thus, parthanatos was the predominant mode of cell death induced by J4 and J6, which explains the high cytotoxicity in CCRF-CEM and CEM/ADR5000 cells. J4 and J6 may be interesting drug candidates and deserve further investigations to overcome resistance of tumors against apoptosis. This study will promote the design of further novel palladium (II)-based complexes as chemotherapeutic agents. © 2023 Elsevier B.V.
Mosallaei, H. ,
Hadadzadeh h., H. ,
Foelske, A. ,
Sauer, M. ,
Amiri rudbari, H. ,
Blacque, O. Publication Date: 2022
Dalton Transactions (14779226) 51(16)pp. 6314-6331
Water electrolysis is one of the most capable processes for supplying clean fuel. Herein, two novel ionic Ru(ii)-Fe(ii) complexes, [Ru(tmphen)3]2[Fe(CN)6] and [Ru(phen)3][Fe(CN)5(NO)], where tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline and phen = 1,10-phenanthroline, were synthesized and characterized by UV-Vis spectroscopy, elemental analysis, FT-IR, and single-crystal X-ray structural analysis. By thermally decomposing the [Ru(tmphen)3]2[Fe(CN)6] complex at 600 °C for 4 h, a heterostructured RuO2-Fe2O3 nanocomposite was fabricated through a facile one-pot treatment and then characterized by FT-IR, XRD, FT-Raman, UV-Vis (DRS), ICP-OES, FE-SEM, TEM, TGA/DTG, BET, and XPS analyses, which revealed the formation of highly crystalline RuO2-Fe2O3 nanoparticles with an average size of 8-12 nm. The prepared nanocomposite was an efficient heterostructured electrocatalyst for performing water-splitting redox reaction processes, including hydrogen and oxygen evolution reactions (HER and OER) in alkaline solutions. In this regard, RuO2 and Fe2O3 samples were also prepared through thermal decomposition of [Ru(tmphen)3](NO3)2 and K4[Fe(CN)6] precursors, respectively, as control experiments to compare their HER and OER electrocatalytic activity with that of the RuO2-Fe2O3 nanocomposite. Specifically, the RuO2-Fe2O3 nanocomposite exhibited significant electrocatalytic performance, generating 10 mA cm−2 current density at −148 and 292 mV overpotentials, and the Tafel slope results from fitting the LSV curves to the Tafel equation were −43 and 56.08 mV dec−1 for the HER and OER, respectively. Therefore, the heterostructured RuO2-Fe2O3 nanocomposite can be viewed as a bi-functional electrocatalyst for HER and OER because it exploits the synergistic effects of heterostructures and active sites at its interface. © 2022 The Royal Society of Chemistry.
Kargar, H. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Ardakani, A.A. ,
Sedighi-khavidak, S. ,
Munawar, K.S. ,
Ashfaq, M. ,
Tahir, M.N. Publication Date: 2022
Inorganica Chimica Acta (18733255) 530
Binuclear zinc(II) Schiff base complexes were synthesized through the reaction of ONNO tetradentate Schiff base ligands derived from the condensation of 2,2-dimethyl-1,3-propanediamine and 5-chlorosalicylaldehyde or 5-bromosalicylaldehyde with zinc acetylacetonate salt. The structures of synthesized products were explored spectroscopically through the FT-IR, 1H NMR and elemental analysis. Structural analysis of the complexes revealed that the compound is a centrosymmetric dimer in which the five coordinated Zn(II) atoms are linked to the opposite metal center by making μ-phenoxo bridges through one of the phenolic oxygen atoms of Schiff base ligands. The nature and types of non-covalent interactions present among the sample molecules were also investigated by using the quantum theory of atoms in molecules and non-covalent interactions calculations. The theoretical calculations, performed by density functional theory using the B3LYP/Def2-TZVP level of theory, direct that the intended outcomes are in compliance with the actual consequences. Furthermore, from antimicrobial screenings it was revealed that the zinc complexes are more active as compared to the ligands. © 2021 Elsevier B.V.
Saadati, A. ,
Amiri rudbari, H. ,
Aryaeifar, M. ,
Blacque, O. ,
Correia, I. ,
Islam, M.K. ,
Woschko, D. ,
Haj hassani sohi, T. ,
Janiak, C. ,
Enamullah, M. Publication Date: 2022
CrystEngComm (14668033) 25(3)pp. 365-377
In this study, three pairs of pseudotetrahedral C2-symmetrical bis[(S or R)-N-1-(phenyl)ethyl-(2,4-X1,X2-salicylaldiminato-κ2N,O)]-Δ/Λ-nickel(ii), Δ/Λ-NiSL1-3 or Λ/Δ-NiRL1-3 (X1, X2 = Cl, Cl; Br, Br; Cl, Br) with Δ- or Λ-chirality induction at-metal were synthesized, respectively. X-ray molecular structures showed the formation of a N2O2-chromophore around nickel(ii) from two molecules of Schiff bases in a pseudotetrahedral geometry. The structural analysis further suggested the isolation of opposite configured Δ-Ni and Λ-Ni diastereomers for S- and R-HL1-3 Schiff base ligands in an enantiopure crystal, resulting from diastereoselection and chirality induction at-metal. The gas-phase optimized structures for Δ-NiSL1-3 or Λ-NiRL1-3 are also slightly more stable by 0.10-1.70 kcal mol−1. Electronic circular dichroism (ECD) spectra showed expected mirror-image relationships with opposite Cotton effects, confirming the enantiopurity or enantiomeric excess of NiRL1-3 and NiSL1-3 complexes in solutions. Combined analyses of experimental and simulated ECD spectra suggested diastereomeric excess of Δ-NiSL1-3 or Λ-NiRL1-3 in solutions, demonstrating the preservation of chirality induction at-metal alike in solid or gas phases. The analysis of supramolecular packing explored several kinds of intermolecular interactions with the strongest one for halogen⋯oxygen atoms and only halogen at the para-position of salicylaldehyde is involved in these interactions with Br⋯O > Cl⋯O. Hirshfeld surface analysis also supported such kind of interactions at a distance shorter than the sum of the van der Waals radii. The non-covalent interaction (NCI) indices explored the presence of weak attractive interactions resulting from the halogen atoms of the respective structures. The experimental and simulated PXRD patterns revealed a fair matching, confirming the phase purity of bulk crystal samples of these complexes. © 2023 The Royal Society of Chemistry.
Amiri rudbari, H. ,
Kordestani, N. ,
Cuevas-vicario, J.V. ,
Zhou, M. ,
Efferth, T. ,
Correia, I. ,
Schirmeister, T. ,
Barthels, F. ,
Enamullah, M. ,
Fernandes, A.R. Publication Date: 2022
New Journal of Chemistry (11440546) 46(14)pp. 6470-6483
In continuation of our work on the synthesis of heteroleptic enantiopure Pd(ii)-complexes, four mixed-ligand enantiomeric pairs of Pd(ii) complexes (J1-J8), [Pd(pic) (R or S)-N-(2,3-dihydroxypropyl)-3,5-X1,X2-salicylaldimines]NO3, (pic = 2-picolylamine; X1 = X2 = Cl, Br, I; X1/X2 = Br/Cl), were synthesized by the reaction of enantiopure halogen-substituted Schiff bases (R or S)-N-(2,3-dihydroxypropyl)-3,5-X1,X2-salicylaldimines with [Pd(pic)Cl2] and obtained as yellow precipitates. The composition and structure of the complexes were confirmed by means of elemental analyses, NMR (1H and 13C), FT-IR spectroscopy and theoretical calculations. The NMR data confirmed the stability of these complexes in DMSO. The electronic structure of the reported complexes was investigated using UV-Vis absorption and electronic circular dichroism (ECD) spectroscopy. The antiproliferative activity of the newly synthesized metal complexes was evaluated against CCRF-CEM acute lymphocytic leukemia cells and their multidrug-resistant CEM/ADR5000 subline showing IC50 values in the low-micromolar range. The two most active compounds (J4 and J6) in the assays above were selected for further biological testing, i.e. cell cycle analyses, apoptosis detection and ability to inhibit the chymotrypsin-like activity of the 20S human proteasome. Both compounds arrested the G2/M cell cycle phase in a concentration-dependent manner without inducing significant apoptosis and inhibited the above-mentioned proteolytic activity of the proteasome in the low-micromolar range. © 2022 The Royal Society of Chemistry
Kargar, H. ,
Moghimi, A. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Munawar, K.S. Publication Date: 2022
Journal of Sulfur Chemistry (17415993) 43(1)pp. 22-36
A new ONO-tridentate Schiff base ligand (H2L) derived by the condensation of nicotinic hydrazide with 5-chlorosalicylaldehyde has been prepared and characterized by combustion analysis (CHN), FT-IR and multinuclear (1H and 13C) NMR spectroscopy. The crystalline nature and molecular structure of the ligand were confirmed by single-crystal X-ray diffraction analysis. Furthermore, the optimized structural parameters of the four possible configurations of the ligand including Z and E stereoisomers each containing two tautomeric forms (enol and keto) have also been investigated. The theoretical parameters were calculated by performing the DFT method using the B3LYP/Def2-TZVP level of theory. In addition to this, dioxomolybdenum(VI) (MoO2L) and oxovanadium(V) (VOL) complexes with the entitled Schiff base ligand have also been prepared and characterized by different techniques. Then, the catalytic efficiencies of synthesized VOL and MoO2L complexes were also explored for the oxidation of sulfides using 30% aqueous H2O2 as a source of oxygen. These homogeneous catalysts showed excellent catalytic activities in the oxidation of both aromatic and aliphatic sulfides. © 2021 Informa UK Limited, trading as Taylor & Francis Group.
Publication Date: 2022
Australian Journal of Chemistry (14450038) 75(3)pp. 181-196
The nucleophilic ability of substituted 5-aminopyrazoles and the type of dicarbonyl component were investigated to synthesise various pyrazolodihydropyridines and pyrazolodihydropyrimidines. In this multicomponent reaction, two possible reaction mechanisms are proposed to elucidate the importance of the nucleophilic positions in the 5-aminopyrazole molecule leading to the different cyclocondensation products. The extent of the nucleophilicity of the C4-position (β-position of the enamine moiety), the lone pairs of the N1-atom and the NH2 group in the pyrazole molecule affect the reaction time and type of product formed. The acidity of the CH2 moiety of the β-dicarbonyl compound may affect the type of product formed. 1H and 13C NMR data and the X-ray crystal structure analysis support the experimental work and the formed product type. © 2022
Amiri rudbari, H. ,
Saadati, A. ,
Aryaeifar, M. ,
Blacque, O. ,
Cuevas-vicario, J.V. ,
Cabral, R. ,
Raposo, L.R. ,
Fernandes, A.R. Publication Date: 2022
Bioorganic Chemistry (00452068) 119
In order to better understand the effect of structure, halogen substitution, metal ions and ligand flexibility on antiproliferative activity, eight Cu(II) complexes and eight Pt(II) complexes were obtained of 2,4-X1,X2-6-((pyridine-2-ylmethylamino)methyl)phenol and 2,4-X1,X2-6-((pyridine-2-ylmethylamino)ethyl)phenol (where X is Cl, Br, or I) ligands. The compounds were characterized with various techniques, such as FT-IR, NMR, elemental analysis and single-crystal X-ray diffraction (SCXRD). The X-ray structures showed that ligand acts as a bidentate and tridentate donor in Cu(II) and Pt(II) complexes, respectively. This difference in structures is due to the use or non-use of base in the preparation of complexes. Also, complexation of Cl2-H2L1 with CuCl2·2H2O gives two different types of structures: polymer (Cl2-H2L1-Cupolymer) and dimer (Cl2-H2L1-Cudimer), according to the crystal color. In addition, 1H NMR spectrum for platinum complexes display two set of signals that can be attributed to the presence of two isomers in solution. All complexes induced moderate to high reduction in A2780 and HCT116 cancer cell viability. However, only complexes bearing iodo- substituted in ligands exhibited significantly low cytotoxicity in normal fibroblasts when compared with cancer cell lines. The antiproliferative effect exhibited by I2-H2L2-Cu complex in A2780 cell line was due to induction of cell death mechanisms, namely by apoptosis and autophagy. I2-H2L2-Cu complex does not cause DNA cleavage but a slight delay in cell cycle was observed for the first 24 h of exposition. High cytotoxicity was related with the induction of intracellular ROS. This increase in intracellular ROS was not accompanied by destabilization of the mitochondrial membrane which is an indication that ROS are being triggered externally by I2-H2L2-Cu complex and in agreement with an extrinsic apoptosis activation. I2-H2L2-Cu complex has a pro-angiogenic effect, increasing the vascularization of the CAM in chicken embryos. This is also a very important characteristic in cancer treatment since the increased vascularization in tumors might facilitate the delivery of therapeutic drugs. Taken together, these results support the potential therapeutic of the I2-H2L2-Cu complex. © 2021 Elsevier Inc.
Amiri rudbari, H. ,
Saadati, A. ,
Aryaeifar, M. ,
Blacque, O. ,
Correia, I. ,
Islam, M.K. ,
Woschko, D. ,
Janiak, C. ,
Enamullah, M. Publication Date: 2022
Dalton Transactions (14779226) 51(6)pp. 2385-2399
Reactions of enantiopure (S or R)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldimine (S-H or R-H; X1, X2 = dihalogen) with Zn(ii)-nitrate give bis[(S or R)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldiminato-κ2N,O]-zinc(ii), (Δ-ZnS or Λ-ZnR) with Δ/Λ-chirality induction at-metal in the C2-symmetric molecules. EI-mass spectra show parent ion peaks. X-ray structures indicate that two phenolate-oxygen and two imine-nitrogen atoms from two molecules of the Schiff bases coordinate to the Zn(ii) ion in a pseudotetrahedral geometry. Structural analyses give evidence that the S- or R-ligand chirality gives only one diastereomer Δ-ZnS or Λ-ZnR in an enantiopure crystal. Gas-phase optimized structures suggest that the Δ-ZnS or Λ-ZnR diastereomers are slightly more stable than Λ-ZnS or Δ-ZnR by 1-2 kcal mol-1. The intramolecular interactions were analyzed with the Independent Gradient Model (IGM) using the program Multiwfn on the optimized structures and also indicate the diastereomeric preference of Δ-ZnS1 over Λ-ZnS1 (or Λ-ZnR1 over Δ-ZnR1). Variable time and temperature 1H NMR spectra support the presence of only one diastereomer Λ-ZnR or Δ-ZnS in the bulk samples, backed by the simulated spectra which exhibit no diastereomerization in solution. In contrast, the reported Zn(ii)-(R or S)-salicylaldiminato/naphthaldiminato complexes show a diastereomeric mixture of both Δ- and Λ-forms and a Δ ⇄ Λ equilibrium in solution. Electronic circular dichroism (ECD) spectra in solution display expected mirror-image relationships for the (S or R)-Schiff base ligands and the (S or R)-ligated complexes. Combined analyses of experimental and simulated ECD spectra further support the notion of diastereomeric excess of Δ-ZnS or Λ-ZnR in solution. The overall results thus suggest the preservation of chirality at-zinc induced by S- or R-ligands in a solid or solution. Supramolecular packing analyses explore different kinds of intermolecular interactions with the strongest one for X⋯O. Only the halogen atom in the para position is involved in these interactions with Br⋯O > Cl⋯O. Hirshfeld surface analyses also support these interactions between two molecules at a distance shorter than the sum of the vdW radii. Comparison of the experimental and simulated PXRD patterns from the single-crystal X-ray structures shows a good matching and confirms the phase purity of the bulk samples. This journal is © The Royal Society of Chemistry.
Takjoo, R. ,
Ramasami, P. ,
Rhyman, L. ,
Ahmadi, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2022
Journal of Molecular Structure (00222860) 1255
Iron(III) and copper(II) complexes with an allyl N'-(1-(2-hydroxyphenyl)ethylidene)carbamohydrazonothioate·hydrobromide (H2L) and ethyl N'-5‑bromo-2-hydroxybenzylidenecarbamohydrazonothioate·hydrobromide (H2L') ligands were synthesized and characterized by elemental analysis, FT-IR spectroscopy and molar conductivity. Single crystal X-ray crystallography reveals that the iron and copper complexes have square pyramidal and square planar geometries, respectively. The ligands act as a binegative tetradentate chelating agent and they are bonded to the metal center through the phenolic oxygen, isothioamide nitrogen, and azomethine nitrogen atoms. The fifth site of the Fe(III) coordination sphere in both Fe complexes is occupied by chloride ion. Density functional theory method was used to complement the structural and spectroscopic data obtained experimentally. We also performed docking calculations of the complexes with human serum albumin and the copper complex binds preferentially. © 2022 Elsevier B.V.
Kargar, H. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Adabi ardakani, A. ,
Sedighi-khavidak, S. ,
Munawar, K.S. ,
Ashfaq, M. ,
Tahir, M.N. Publication Date: 2022
Polyhedron (02775387) 213
Two new zinc(II) Schiff base complexes (Z1 and Z2) are prepared by treating ONNO tetradentate Schiff base ligands (H2L1 = [6,6′-((1E,1′E)-((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol)] and H2L2 = [2,2′-((1E,1′E)-((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(4-methoxyphenol)]) with acetylacetonate salt of zinc. The synthesized Schiff base ligands and their respective zinc(II) complexes were characterized by elemental analysis (CHN) and various spectroscopic techniques like FT-IR and 1H NMR. The single crystal X-ray structures of Z1 and Z2 show the effect of salicylidene ligand on the nature of mono and dinuclear Zn(II) Schiff base complexes. In Z1 complex, a square pyramidal geometry is adapted by the complex, supported by the ONNO donor atoms of the tetradentate Schiff base and a coordinated water molecule. Structural analysis of Z2 complex revealed that the compound is a centrosymmetric dimer in which the five coordinated Zn(II) atoms are linked to the opposite metal center by making μ-phenoxo bridges through one of the phenolic oxygen atoms of Schiff base ligands. The nature of various kinds of non-covalent interactions present among the sample molecules was also investigated by using QTAIM and NCI calculations. The theoretical calculations were performed by DFT using the B3LYP/Def2-TZVP level of theory, which indicated that the intended outcomes are in compliance with the actual consequences. Furthermore, the antibacterial potential of the Schiff base ligands and their corresponding zinc complexes was measured by testing them against two Gram-positive (Staphylococcus aureus and Bacillus cereus) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacterial strains. The agar well diffusion method and poisoned media technique were used for screening of bacterial and fungal species, respectively. According to the results of the zone of inhibition assessments, metal complexes have comparatively more inhibition potential relative to free ligands. © 2021 Elsevier Ltd
Taghizadeh shool, M. ,
Amiri rudbari, H. ,
Gil-antón, T. ,
Cuevas-vicario, J.V. ,
García, B. ,
Busto, N. ,
Moini, N. ,
Blacque, O. Publication Date: 2022
Dalton Transactions (14779226) 51(19)pp. 7658-7672
Ru(ii) polypyridyl complexes are widely used in biological fields, due to their physico-chemical and photophysical properties. In this paper, a series of new chiral Ru(ii) polypyridyl complexes (1-5) with the general formula {Δ/Λ-[Ru(bpy)2(X,Y-sal)]BF4} (bpy = 2,2′-bipyridyl; X,Y-sal = 5-bromosalicylaldehyde (1), 3,5-dibromosalicylaldehyde (2), 5-chlorosalicylaldehyde (3), 3,5-dichlorosalicylaldehyde (4) and 3-bromo-5-chlorosalicylaldehy (5)) were synthesized and characterized by elemental analysis, FT-IR, and 1H/13C NMR spectroscopy. Also, the structures of complexes 1 and 5 were determined by X-ray crystallography; these results showed that the central Ru atom adopts a distorted octahedral coordination sphere with two bpy and one halogen-substituted salicylaldehyde. DFT and TD-DFT calculations have been performed to explain the excited states of these complexes. The singlet states with higher oscillator strength are correlated with the absorption signals and are mainly described as 1MLCT from the ruthenium centre to the bpy ligands. The lowest triplet states (T1) are described as 3MLCT from the ruthenium center to the salicylaldehyde ligand. The theoretical results are in good agreement with the observed unstructured band at around 520 nm for complexes 2, 4 and 5. Biological studies on human cancer cells revealed that dihalogenated ligands endow the Ru(ii) complexes with enhanced cytotoxicity compared to monohalogenated ligands. In addition, as far as the type of halogen is concerned, bromine is the halogen that provides the highest cytotoxicity to the synthesized complexes. All complexes induce cell cycle arrest in G0/G1 and apoptosis, but only complexes bearing Br are able to provoke an increase in intracellular ROS levels and mitochondrial dysfunction. © 2022 The Royal Society of Chemistry
Publication Date: 2021
RSC Advances (20462069) 11(6)pp. 3655-3665
A novel porous organic polymer (denoted by Q-POP) was successfully fabricated by free-radical copolymerization of allyl-substituted 2,3-di(2-hydroxyphenyl)1,2-dihydroquinoxaline, and divinylbenzene under solvothermal conditions and used as a new platform for immobilization of copper nanoparticles. The CuNPs@Q-POP nanocatalyst was prepared via incorporating of Cu(NO3)2 into the polymeric network, followed by the reduction of Cu2+ ion with hydrazine hydrate. The obtained materials were characterized through FT-IR, XRD, N2 adsorption-desorption isotherms, ICP, TGA, SEM, HR-TEM, EDX, and the single-crystal X-ray crystallography. The results displayed that Q-POP and CuNPs@Q-POP possessed high surface area, hierarchical porosity, and excellent thermal and chemical stability. The as-synthesized catalyst was utilized for the Ullmann C-N coupling reaction of aromatic amines and different aryl halides to prepare various diarylamine derivatives. All types of aryl halides (except aryl fluorides) were screened in the Ullmann C-N coupling reaction with aromatic amines to produce diaryl amines in good to excellent yields (50-98%), and it turned out that aryl iodides have the best results. Besides, due to the strong interactions between CuNPs, N, and O-atoms of quinoxaline moiety existing in the polymeric framework, the copper leaching from the support was not observed. Furthermore, the catalyst was recycled and reused for five consecutive runs without significant activity loss. © The Royal Society of Chemistry.
Kordestani, N. ,
Amiri rudbari, H. ,
Fateminia, Z. ,
Caljon, G. ,
Maes, L. ,
Mineo, P.G. ,
Cordaro, A. ,
Mazzaglia, A. ,
Scala, A. ,
Micale, N. Publication Date: 2021
Applied Organometallic Chemistry (02682605) 35(2)
A series of polymeric silver(I) complexes with Schiff base ligands containing pyridine and 3,5-halogen substituted phenol moieties were synthesized and characterized by spectroscopic methods and in the case of Ag6 also by X-ray crystallography. All silver(I) complexes (Ag1–Ag8) were evaluated for their biological activity against a panel of pathogens including the protozoa Trypanosoma cruzi, T. brucei, T. rhodesiense and Leishmania infantum; the bacteria Staphylococcus aureus, Escherichia coli, Mycobacterium tuberculosis H37Ra and the yeast Candida albicans. Cytotoxicity evaluation was carried out on human lung fibroblasts (MRC-5) and on primary peritoneal mouse macrophages. The most relevant result reveals antileishmanial activity potential with all complexes demonstrating higher potency than the reference drug miltefosine. Complexes with the best antiprotozoal profile (i.e., Ag2 and Ag7) were selected for incorporation into poly (lactic acid) nanoparticles (PLA NPs) with the aim to enhance selectivity. PLA/Ag2 NPs and PLA/Ag7 NPs exhibited adequate physicochemical properties, that is, average size of 263 ± 60 nm and 225 ± 6 nm, respectively, good entrapment efficiency (69% and 63%), loading content (6.2% and 5.7%) and stability. The cytotoxicity of PLA/Ag2 NPs and PLA/Ag7 NPs on MRC-5 cells was reduced with respect to the “free” metal complexes by ~2-fold and ~6-fold, respectively. © 2020 John Wiley & Sons, Ltd.
Kordestani, N. ,
Amiri rudbari, H. ,
Fernandes, A.R. ,
Raposo, L.R. ,
Luz, A. ,
Baptista, P.V. ,
Bruno, G. ,
Scopelliti, R. ,
Fateminia, Z. ,
Micale, N. Publication Date: 2021
Dalton Transactions (14779226) 50(11)pp. 3990-4007
To investigate the effect of different halogen substituents and leaving groups and the flexibility of ligands on the anticancer activity of copper complexes, sixteen copper(ii) complexes with eight different tridentate Schiff-base ligands containing pyridine and 3,5-halogen-substituted phenol moieties were synthesized and characterized by spectroscopic methods. Four of these complexes were also characterized by X-ray crystallography. The cytotoxicity of the complexes was determined in three different tumor cell lines (i.e.the A2780 ovarian, HCT116 colorectal and MCF7 breast cancer cell line) and in a normal primary fibroblast cell line. Complexes were demonstrated to induce a higher loss of cell viability in the ovarian carcinoma cell line (A2780) with respect to the other two tumor cell lines, and therefore the biological mechanisms underlying this loss of viability were further investigated. Complexes with ligandL1(containing a 2-pycolylamine-type motif) were more cytotoxic than complexes withL2(containing a 2-(2-pyridyl)ethylamine-type motif). The loss of cell viability in A2780 tumor cells was observed in the orderCu(Cl2-L1)NO3>Cu(Cl2-L1)Cl>Cu(Br2-L1)Cl>Cu(BrCl-L1)Cl. All complexes were able to induce reactive oxygen species (ROS) that could be related to the loss of cell viability. ComplexesCu(BrCl-L1)ClandCu(Cl2-L1)NO3were able to promote A2780 cell apoptosis and autophagy and for complexCu(BrCl-L1)Clthe increase in apoptosis was due to the intrinsic pathway.Cu(Cl2-L1)ClandCu(Br2-L1)Clcomplexes lead to cellular detachment allowing to correlate with the results of loss of cell viability. Despite the ability of theCu(BrCl-L1)Clcomplex to induce programmed cell death in A2780 cells, its therapeutic window turned out to be low making theCu(Cl2-L1)NO3complex the most promising candidate for additional biological applications. © The Royal Society of Chemistry 2021.
Amiri rudbari, H. ,
Saadati, A. ,
Aryaeifar, M. ,
Correia, I. ,
Marques, F. ,
Blacque, O. ,
Micale, N. Publication Date: 2021
Bioorganic and Medicinal Chemistry Letters (14643405) 49
The reaction of potentially N,N,O-tridentate Schiff base ligands, Cl-LH, Br-LH, BrCl-LH and H-LH, with [VIVO(acac)2] in 2:1 ratio in methanol gave the corresponding mononuclear and dinuclear oxidovanadium(IV) complexes, VO(Cl-L)2 (1), VO(Br-L)2 (2), [(BrCl-L)2(H2O)V(μ-O)VO(BrCl-L)2] (3) and [(H-L)2(H2O)V(μ -O)VO(H-L)2] (4), in good yields. The ligands and complexes were fully characterized by elemental analysis and FT-IR spectroscopy. The ligands were also characterized by 1H NMR spectroscopy. The oxidation state of V(IV)O with d1 configuration in all synthesized complexes was confirmed by EPR. Moreover, the structures of 2 and 3 were determined by X-ray diffraction (XRD) analysis which revealed them as mono- and dinuclear vanadium(IV) complexes, respectively, with the ligands coordinated as bidentate chelates. The structure of 3 represents the first example of dinuclear V(IV) complex with O → VIV = O → VIV = O core (Cambridge Structural Database (CSD), version 5.42, update of May 2021). The cytotoxicity of ligands and complexes was evaluated towards ovarian (A2780), breast (MCF7) and prostate (PC3) cancer cells at 48 h. While ligands showed modest IC50 values (>42 μM), all complexes turned out to be effective in the range 3.9–17.2 μM. In particular, A2780 and MCF7 cell lines were the most sensitive to the newly synthesized V(IV)O complexes. © 2021 Elsevier Ltd
Kordestani, N. ,
Amiri rudbari, H. ,
Correia, I. ,
Valente, A. ,
Côrte-real, L. ,
Islam, M.K. ,
Micale, N. ,
Braun, J.D. ,
Herbert, D.E. ,
Tumanov, N. Publication Date: 2021
New Journal of Chemistry (11440546) 45(20)pp. 9163-9180
Seven enantiomeric pairs of palladium complexes, [Pd(pic)(R or S)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldiminate)]NO3, [Pd(pic)(R or S)]NO3 (X1 = X2 = Cl, Br, I, H; X1/X2 = Br/Cl), were synthesized by the reaction of enantiopure halogen-substituted Schiff bases (R or S)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldimine with [Pd(pic)Cl2] (pic = 2-picolylamine). The composition and structure of the complexes were confirmed by means of FT-IR, 1H NMR and 13C NMR spectroscopy, elemental analysis and X-ray crystallography. The electronic structure of the reported complexes was investigated using UV-vis absorption and electronic circular dichroism (ECD) spectroscopy, complemented by DFT/TDDFT modelling. To investigate the effect of chirality and different halogen substituents on the anticancer activity of the complexes, the cytotoxic activity of all fourteen complexes was tested in the human breast cancer cell lines MDA-MB-231 and MCF-7 at 24 h using the colorimetric MTT assay. Also, the cell death mechanism was assessed using the annexin V/propidium iodide (AV/PI) cytometry-based assay. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Taherzadeh, M. ,
Pourayoubi, M. ,
Alviri, B.V. ,
Bayraq, S.S. ,
Ariani, M. ,
Nečas, M. ,
Dušek, M. ,
Eigner, V. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2021
Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials (20525206) 77pp. 307-308
For [C(O)NH](N)2P(O)-based structures, the magnitude of the differences in the N—H. . .O, H. . .O P and H. . .O C angles has been evaluated when the N—H bond lengths, determined by X-ray diffraction, were compared to the neutron normalized values and the maximum percentage difference was obtained, i.e. about 3% for the angle even if the N—H bond lengths have a difference of about 30% (0.7 Å for the X-ray and 1.03 Å for the neutron-normalized value). The symmetries of the crystals are discussed with respect to the symmetry of the molecules, as well as to the symmetry of hydrogen-bonded motifs, and the role of the most directional hydrogen bond in raising the probability of obtaining centrosymmetric crystal structures is investigated. The work was performed by considering nine new X-ray crystal structures and 204 analogous structures retrieved from the Cambridge Structural Database. © 2021 International Union of Crystallography.
Kargar, H. ,
Forootan, P. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Munawar, K.S. ,
Ashfaq, M. ,
Tahir, M.N. Publication Date: 2021
Inorganica Chimica Acta (18733255) 523
Two new oxovanadium and dioxomolybdenum Schiff base complexes, [VvO(L)(OCH3)(CH3OH)] and [MoVIO2(L)(CH2CH3OH)], were synthesized by treating an ONO-donor type Schiff base ligand (H2L) derived by condensation of 5-nitrosalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum, [VO(acac)2 and MoO2(acac)2], respectively. The synthesized ligand and complexes were characterized by various spectroscopic techniques like FT-IR, multinuclear (1H, 13C) NMR, elemental analysis and the most authentic single crystal X-ray diffraction analysis. In both complexes the geometry around the central metal ions was distorted octahedral as revealed by the data collected from diffraction studies. Theoretical calculation of the synthesized compounds were carried out by DFT as well as TD-DFT using B3LYP method by employing the Def2-TZVP basis set. The findings of theoretical data indicated that the calculated results are in accordance with the experimental findings. Moreover, the catalytic efficiencies of both complexes were investigated by oxidizing the benzylic alcohols in the presence of urea hydrogen peroxide (UHP) in acetonitrile. © 2021 Elsevier B.V.
Kargar, H. ,
Kaka-naeini, A. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Munawar, K.S. Publication Date: 2021
Journal of Coordination Chemistry (10290389) 74(9-10)pp. 1563-1583
New oxovanadium and dioxomolybdenum Schiff base complexes, [VO(L)(OCH3)] n and [MoO2(L)(CH3OH)], were synthesized by treating an ONO donor Schiff base (H2L) derived by condensation of 3-ethoxysalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum (VO(acac)2 and MoO2(acac)2), respectively. The synthesized ligand and complexes were characterized by FTIR, multinuclear (1H, 13C) NMR, elemental and single crystal X-ray diffraction analysis. In both complexes, the geometry around the central metal ions was distorted octahedral as revealed by diffraction studies. Theoretical calculations of the synthesized compounds were carried out by DFT at B3LYP/Def2-TZVP level of theory, which showed good correlation with the experimental results. Moreover, the catalytic efficiency of both complexes was investigated by oxidizing aryl and alkyl sulfides in the presence of 30% H2O2 in ethanol. © 2021 Informa UK Limited, trading as Taylor & Francis Group.
Aryaeifar, M. ,
Amiri rudbari, H. ,
Blacque, O. ,
Islam, M.K. ,
Scopelliti, R. ,
Braun, J.D. ,
Herbert, D.E. ,
Bruno, G. ,
Janiak, C. ,
Enamullah, M. Publication Date: 2021
CrystEngComm (14668033) 23(36)pp. 6322-6339
1,2-Bis(2′-nitrophenoxy)-3-R-benzenes {R = H (1), CH3(2) and OCH3(3)} have been prepared from the SNAr reaction between 1-fluoro-2-nitrobenzene and 3-R-catechol (aromatic diol), and are then reduced to the corresponding diamines 1,2-bis(2′-aminophenoxy)-3-R-benzene {R = H (4), CH3(5) and OCH3(6)}, respectively. Reaction of these diamines with 2-hydroxy-1-naphthaldehyde gives tetradentate Schiff base ligands {H2L: R = H (H2L1), CH3(H2L2) and OCH3(H2L3)}, respectively. The Schiff base ligands coordinate to metal(ii) ions to provide the complexesML1,ML2andML3(M = Cu and Zn), respectively. X-ray molecular structure determinations were performed to explore stereochemical rigidity as the origin of chirality induction in the dinitro (2), diamine (5) and Schiff base ligands (H2L1andH2L2) as well as in the complexes (ZnL2,ZnL3andCuL3), respectively. The structures feature an N2O2-chromophore from bis(2-oxo-1-naphthaldiminate) moieties with one additional weak Cu/Zn⋯O (ether) contact to give a 4 + 1 coordination with a distorted square-pyramidal geometry forZnL2,ZnL3andCuL3, respectively. Without considering this additional contact, the structures are distorted tetrahedral or distorted square-planar for the Zn or Cu complexes, such that a chiral Λ- and Δ-configuration at the metal atom is induced. All three metal complexes crystallize as a crystalline racemate or racemic mixture ofΛ/Δ-ML. The supramolecular packing in the structures is organized by inter-/intra-molecular π-π and C-H⋯π interactions, respectively. The optimized structures and excited state properties from DFT/TDDFT calculations support the experimental results. © The Royal Society of Chemistry 2021.
Publication Date: 2021
Polyhedron (02775387) 205
Four new azo-Schiff base ligands were prepared (H2La-H2Ld) via condensation of Methyl-2-{N-(2′-aminoethane)}-amino-1-cyclopentenedithiocarboxylate (Hcden) with derivatives of (E)-2-hydroxy-5-(phenyldiazenyl)benzaldehyde. The corresponding nickel(II) complexes were also synthesized. The structures of the azo-Schiff base ligands and the complexes were characterized by elemental analyses, UV–Vis, IR and 1HNMR spectroscopies. The structures of [NiLa] and [NiLc] complexes have been determined by X-ray crystallography. The Ni(II) metal complexes are formed by the coordination of the N, S and O atoms of the ligands. The X-ray results confirm that the geometry of the Ni(II) metal complexes are slightly distorted square-planar structures. © 2021
Kargar, H. ,
Bazrafshan, M. ,
Fallah-mehrjardi, M. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Munawar, K.S. ,
Ashfaq, M. ,
Tahir, M.N. Publication Date: 2021
Polyhedron (02775387) 202
For the first time, two new oxovanadium and dioxomolybdenum Schiff base complexes, VOL(OMe) and MoO2L, were synthesized through the reaction of a ONO tridentate Schiff base ligand (H2L) derived from the condensation of 5-bromosalicylaldehyde and nicotinic hydrazide with oxo and dioxo acetylacetonate salts of vanadium and molybdenum, [VO(acac)2 and MoO2(acac)2], respectively. The synthesized ligand and complexes were characterized by various spectroscopic techniques like FT-IR, 1H NMR, 13C NMR, elemental analysis (CHN) and the most authentic single crystal X-ray diffraction analysis (SC-XRD). The geometry around the central metal ion in MoO2L was distorted octahedral as revealed by the data collected from diffraction studies. Non-covalent interactions that are responsible for crystal packing are explored by Hirshfeld surface analysis. Theoretical calculations of the synthesized compounds, carried out by DFT at B3LYP/Def2-TZVP level of theory, indicated that the calculated results are in agreement with the experimental findings. Moreover, the catalytic activities of both complexes were investigated for the selective oxidation of benzylic alcohols using urea hydrogen peroxide (UHP) in acetonitrile. © 2021 Elsevier Ltd
Kargar, H. ,
Fallah-mehrjardi, M. ,
Ashfaq, M. ,
Munawar, K.S. ,
Tahir, M.N. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Adabi ardakani, A. ,
Sedighi-khavidak, S. Publication Date: 2021
Journal of Coordination Chemistry (10290389) 74(16)pp. 2720-2740
New zinc(II) Schiff base complexes (Z1 and Z2) were prepared through the treatment of ONNO tetradentate Schiff base ligands (H2L1 and H2L2) with zinc acetylacetonate. Elemental analysis (C, H and N) and other spectroscopic techniques such as FT-IR and 1H NMR were used to characterize the produced ligands and their associated Zn(II) complexes. The structure of Z1 was explored by single crystal X-ray diffraction analysis. The structural investigations of Z1 demonstrate that it exists in the form of a centrosymmetric dimer in which penta coordinated Zn(II) ions are inter connected via µ-phenoxo bridges from one of the phenolic oxygen atoms of each tetradentate Schiff base ligand to the opposite zinc(II) ions. The theoretical calculations, performed by DFT using the B3LYP/Def2-TZVP level of theory, directed that the intended outcomes are in compliance with the actual consequences. The nature and types of non-covalent interactions present among the sample molecules were also investigated by using QTAIM and NCI calculations. Furthermore, antimicrobial activities of the synthesized Schiff base ligands and their respective zinc(II) complexes were also examined against two Gram-positive (Staphylococcus aureus and Bacillus cereus) and two Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria, and two fungal species (Aspergillus brasiliensis and Candida albicans). The agar well diffusion method and poisoned media technique were used for the study of biological properties of bacterial and fungi species, respectively. According to assessments of inhibitory zones, metal chelates are found to be somewhat more efficient than free ligands. © 2021 Informa UK Limited, trading as Taylor & Francis Group.
Kordestani, N. ,
Amiri rudbari, H. ,
Fernandes, A.R. ,
Raposo, L.R. ,
Baptista, P.V. ,
Ferreira, D. ,
Bruno, G. ,
Bella, G. ,
Scopelliti, R. ,
Braun, J.D. Publication Date: 2020
ACS Combinatorial Science (21568952) 22(2)pp. 89-99
A series of Cu(diimine)(X-sal)(NO3) complexes, where the diimine is either 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) and X-sal is a monoanionic halogenated salicylaldehyde (X = Cl, Br, I, or H), have been synthesized and characterized by elemental analysis and X-ray crystallography. Penta-coordinate geometries copper(II) were observed for all cases. The influence of the diimine coligands and different halogen atoms on the antiproliferative activities toward human cancer cell lines have been investigated. All Cu(II) complexes were able to induce a loss of A2780 ovarian carcinoma cell viability, with phen derivatives more active than bpy derivatives. In contrast, no in vitro antiproliferative effects were observed against the HCT116 colorectal cancer cell line. These cytotoxicity differences were not due to a different intracellular concentration of the complexes determined by inductively coupled plasma atomic emission spectroscopy. A small effect of different halogen substituents on the phenolic ring was observed, with X = Cl being the most highly active toward A2780 cells among the phen derivatives, while X = Br presented the lowest IC50 in A2780 cells for bpy analogs. Importantly, no reduction in normal primary fibroblasts cell viability was observed in the presence of bpy derivatives (IC50 > 40 μM). Mechanistically, complex 1 seems to induce a stronger apoptotic response with a higher increase in mitochondrial membrane depolarization and an increased level of intracellular reactive oxygen species (ROS) compared to complex 3. Together, these data and the low IC50 compared to cisplatin in A2780 ovarian carcinoma cell line demonstrate the potential of these bpy derivatives for further in vivo studies. Copyright © 2020 American Chemical Society.
Publication Date: 2020
Catalysis Letters (1572879X) 150(11)pp. 3214-3222
Immobilization of silver nanoparticles (Ag NPs) to improve recyclability is crucial for applications in nanocatalysts. Herein, silver nanoparticles were prepared on copper foil by immersing copper foil in the solution of silver citrate, containing an excess of citric acid. The nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDS), and atomic force microscope (AFM). The catalytic activity of silver nanoparticle on copper was studied in reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) in the presence of excess borohydride. The catalyst can be easily recycled and showed excellent reusability as a conversion higher than 95% was achieved after 30 cycles. Thus, the preparation of nanoparticle aggregates on copper foil has been proven a feasible, straightforward, and effective protocol, which would facilitate the applications of Ag NPs in environmental control. Graphic Abstract: [Figure not available: see fulltext.]. © 2020, Springer Science+Business Media, LLC, part of Springer Nature.
Publication Date: 2020
Polyhedron (02775387) 176
Two new amidic macrocycles, L1 and L2 were synthesized by the condensation reaction of 4-chloro- and pyridine-2,6-dicarbonylchloride with 1,2-bis(2-aminoethoxy)ethane and 1-(2-aminoethyl)piperazine, respectively. The compounds have been fully identified by single-crystal X-ray diffraction. These substances were found to exhibit fluorescence property and remarkable solvatofluorochromism in various organic solvents (ΔλEM = 139 and 141 nm for L1 and L2, respectively). Also, the compounds were tested as fluorescent sensor toward a number of metals and noticeable fluorescence was indicated for them in the presence of Pb2+. Subsequent experiments evaluated the ability of the compounds to detect Pb2+ in PC12 (adrenal pheochromocytoma) cells. The cytotoxicity of the compounds was measured via MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide) method. Cell uptake and biosensing capability were evaluated by treating PC12 cells with mentioned compounds and after that with lead(II) nitrate. Obtained results of MTT experiment and fluorescent images revealed that both compounds at about 0.01 μM possess zero cytotoxicity and have acceptable capability for detecting Pb2+ in tested cells. © 2019 Elsevier Ltd
Landrani, A. ,
Mohammadpoor baltork, I. ,
Mirkhani, V. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Amiri rudbari, H. Publication Date: 2020
RSC Advances (20462069) 10(36)pp. 21198-21205
Dendrimers are of great interest due to their special structural topology and chemical versatility. Owing to their properties, dendrimers have found practical applications in catalytic processes as efficient nanoreactors. Therefore, we herein report an environmentally attractive strategy and highly efficient route for the synthesis of a wide variety of diaryl sulfides using palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer (Pdnp-nSTDP) as a nanoreactor. In this manner, different diaryl or aryl heteroaryl sulfides and bis(aryl/heteroarylthio)benzene/anthracene/pyridine derivatives were preparedviaC-S cross-coupling reactions of aryl halides with diaryl/diheteroaryl disulfides under thermal conditions and microwave irradiation. The catalyst could be easily recovered and reused several times without any significant loss of its activity. © The Royal Society of Chemistry 2020.
Mohammadi, A. ,
Doctorsafaei, A.H. ,
Burujeny, S.B. ,
Amiri rudbari, H. ,
Kordestani, N. ,
Ayati najafabadi, S.A. Publication Date: 2020
Chemical Engineering Journal (13858947) 381
In this study, as a novel strategy to overcome gel formation and coagulation problem of waterborne polyurethane (WPU) dispersions containing silver ions, a Schiff base ligand (SBL) derived from 2,4-dihydroxybenzaldehyde and Bis(3-aminopropyl)amine was synthesized and utilized as chain extender in fabrication of WPUs. The effect of SBL incorporation into WPU chains and subsequent complex formation with Ag ions on the storage stability and particle size of the dispersions were studied. The UV–vis spectroscopy results of prepared dispersions confirmed the formation of Ag NPs within the WPUL/Ag sample through in situ reduction of Ag ions by PTMG (polytetramethylene glycol) polyol as a non-toxic reducing agent. Transmission electron microscopy (TEM) images of WPUL/Ag dispersion demonstrated that the formed Ag NPs exhibited a spherical shape with a size below 10 nm. Furthermore, X-ray diffraction (XRD) analysis of WPUL/Ag film affirmed the presence of Ag NPs within the WPUL matrix. Scanning electron microscopy (SEM) photographs of WPUL/Ag film also displayed a homogeneous dispersion for in situ formed Ag NPs. Antibacterial assays showed an excellent activity for WPUL/Ag film against S. aureus and P. aeruginosa bacteria. Besides, in vitro cytotoxicity studies confirmed that the WPUL/Ag sample possess a good biocompatibility toward L929 cells. © 2019 Elsevier B.V.
Kordestani, N. ,
Amiri rudbari, H. ,
Bruno, G. ,
Rosario, S. ,
Braun, J.D. ,
Herbert, D.E. ,
Blacque, O. ,
Correia, I. ,
Zaman, M.A. ,
Bindu, M.M. Publication Date: 2020
Dalton Transactions (14779226) 49(24)pp. 8247-8264
The enantiopure Schiff bases (R or S)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldimine (X1, X2 = Cl, Br, I) coordinate to copper(ii) and provide pseudotetrahedral bis[(S or R)-N-1-(phenyl)ethyl-(2,4-X1,X2-salicylaldiminato-κ2N,O)]-Δ/Λ-Cu(ii) (Λ/Δ-Cu-R or Δ/Λ-Cu-S). An induced Λ and Δ-chirality at-metal centre has been launched along the C2-axis of the molecule. Steric constraints brought by halogen substituents on the coordinating salicylal ring provide diastereoselectively Λ-Cu-R or Δ-Cu-S as major and Δ-Cu-R or Λ-Cu-S as minor diastereomers at solid-state, as evidenced by X-ray crystal structures and PXRD analyses. These results reveal inversion of induced chirality at-metal in comparison to the similar complexes without halogen substituents on the salicylal ring. Electronic circular dichroism (ECD) spectra show mirror-image relationships, confirming enantiomeric excess of the R or S-ligated complexes in solution. Comparisons of experimental and simulated ECD spectra suggest diastereomeric excess of Δ-Cu-R or Λ-Cu-S in solution which correspond to an inversion from the found solid-state Λ-Cu-R or Δ-Cu-S as major diastereomers. In addition, the optimized gas-phase structures also reveal Δ-Cu-R or Λ-Cu-S as slightly more stable than Λ-Cu-R or Δ-Cu-S. Thus, solid-state versus solution (or gas-phase) studies also indicate an interconversion of induced chirality (helicity inversion) at-metal from Λ-Cu-R or Δ-Cu-S to Δ-Cu-R or Λ-Cu-S. Thermal stability increases with the molecular weight of the complexes following Cl < ClBr < Br < I substituents. Hirshfeld surface analyses explore the strongest halogen (ortho)-halogen (para) interactions between two molecules in Λ-Cu-R3 or Δ-Cu-S3 at a distance shorter than the sum of the van der Waals radii of the two iodine atoms, provide a brilliant red spot on the dnorm surfaces. EPR spectra along with simulation suggest an axial symmetry with gz > gx,y > 2.0 and values for gz/Az ≥ 135 cm indicate pseudotetrahedral geometry for the complexes. This journal is © The Royal Society of Chemistry.
Mansouri, S.G. ,
Zali boeini, H. ,
Zomorodian, K. ,
Khalvati, B. ,
Pargali, R.H. ,
Dehshahri, A. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Chavoshpour, Z. Publication Date: 2020
Arabian Journal Of Chemistry (18785352) 13(1)pp. 1271-1282
A series of novel naphtho[1,2-e][1,3]oxazines bearing arylsulfonamide moiety have been synthesized via a one-pot approach and in a green reaction medium. These new naphtho[1,2-e][1,3]oxazine derivatives have been characterized by their 1H NMR, 13C NMR and the X-ray single crystallography method for compound 7a. All the newly synthesized compounds were examined for their in vitro anticancer activity against breast (MCF-7), colon (HCT116), and B-CLL (Waco3-CD5) cancers. Some of these compounds such as 7j and 7l showed remarkable activities against MCF-7 (breast) and HCT116 (colon) cancers with comparable IC50 (The half maximal inhibitory concentration) values as that of known drugs such as 5-fluorouracil (5-FU). In vitro antimicrobial activities of all compounds were also evaluated against five human pathogenic fungi strains and two bacteria (one gram positive and one gram negative). The best MICs (Minimum Inhibitory Concentrations) were found against the C. albicans. © 2017 King Saud University
Askari, B. ,
Amiri rudbari, H. ,
Valente, A. ,
Bruno, G. ,
Micale, N. ,
Shivalingegowda, N. ,
Krishnappagowda, L.N. Publication Date: 2020
ChemistrySelect (23656549) 5(2)pp. 810-817
Breast cancer is the most common type of cancer in women. In the current study, six transition-metal complexes were reacted with a secondary dithiooxamide (H2-isopropyl2DTO) to obtain the corresponding mononuclear complexes (1-6) and their cytotoxicity was evaluated in two human breast cancer cell lines, i. e. MCF-7 and MDA-MB-231. The characterization of the complexes, [LnM(H-isopropyl2 DTO κ-S,S M)] (LnM=(C5Me5)RhCl, (1); (COD)Rh, (2); (η3-allyl)Pd, (3); (trinpropyl-phosphine)PdCl, (4); (bpy)Pt, (5) and (pph3)PtCl, (6)), and the ion pair form of 1–4, IP1-IP4, were accomplished through NMR spectroscopy and elemental analysis. The structures of 1 and IP1 were also determined by single crystal XRD technique. In vitro cytotoxicity studies in MCF-7 and MDA-MB-231 (IC50 determination) showed that all complexes are cytotoxic for both cell lines, with the exception of 2. Compound 3 was the most cytotoxic in the conditions tested. In addition, the compounds induce cell death by apoptosis and inhibit the formation of colonies, indicating that these compounds could provide promising new lead derivatives for anticancer drug development. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Heydari, R. ,
Motieiyan, E. ,
Abdolmaleki, S. ,
Aliabadi, A. ,
Ghadermazi, M. ,
Bagheri, F. ,
Amiri rudbari, H. Publication Date: 2020
Journal of Coordination Chemistry (10290389) 73(16)pp. 2347-2362
Coordination compound (dmapH)2[Sn(pydc)3]·2H2O (where pydc is pyridine-2,6-dicarboxylate and dmapH is 4-dimethylaminopyridine) was prepared from the reaction between the proton-transfer compound, [dmapH]2[pydc2−] and SnCl4·5H2O metal salt. The structure was fully characterized by single-crystal X-ray diffraction and distorted tricapped triangular prism geometry was realized for it. The thermal behavior of the complex was investigated by TGA-DTA analyses. Then, inhibitory effect of both the complex and its ligand was tested, using oxaliplatin as a standard, under MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide) method, against U251 (a human glioblastoma), H1299 (a human non-small cell lung carcinoma), βTC (a mouse beta pancreatic), A431 (an epidermoid carcinoma) and HFF (a human foreskin fibroblast) cell lines. Potent and selective anti-proliferative effect of the complex (IC50 = 1 μM, MAE = 65.32%) and also intense decrease of mitochondrial membrane potential (MMP) was exhibited on A431 cells. Evaluation of reactive oxygen species (ROS) in cited cells confirmed that apoptotic pathway may be a possible mode for the death of cells. In order to evaluate the cellular internalization potential of the complex, A431 cells were incubated with it at IC50 concentration. The recorded fluorescent images confirmed successful penetration of the complex. © 2020 Informa UK Limited, trading as Taylor & Francis Group.
Molaee, H. ,
Sahihi, M. ,
Moghadam, M. ,
Mirkhani, V. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. ,
Amiri rudbari, H. Publication Date: 2019
Journal of Biomolecular Structure and Dynamics (07391102) 37(3)pp. 641-648
Publication Date: 2019
Journal Of The Iranian Chemical Society (1735207X) 16(6)pp. 1139-1146
A series of 4-amino-functionalized spiropyrimidine-2-thione derivatives were simply produced by the one-pot three-component reaction of alicyclic carbonyl compounds, nitriles containing an acidic methylene, and thiourea in the presence of NaOMe in MeOH. © 2019, Iranian Chemical Society.
Askari, B. ,
Amiri rudbari, H. ,
Micale, N. ,
Schirmeister, T. ,
Maugeri, A. ,
Navarra, M. Publication Date: 2019
Journal of Organometallic Chemistry (0022328X) 900
Three heterobimetallic platinum (II)/ruthenium (II) and platinum (II)/rhodium (III) complexes, A: Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}-[Ru (p-cymene)Cl], R = isoamyl; B: Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}[Rh (phpy)2], R = isoamyl; C: [Pt{S–S2C2(NR)2H}{μ-S2C2(NR)2}-[Rh(C5Me5)Cl]], R = benzyl, were prepared from mononuclear complexes 1 and 2, 1: [Pt (H-isoamyl2DTO)2]; 2: [Pt (H-benzyl2DTO)2], DTO = dithiooxamide, by reaction of 1 or 2 with the corresponding chlorido-bridged dimers, [Rh(C5Me5)Cl (μ-Cl)]2, [Ru (p-cymene)Cl (μ-Cl)]2 or [Rh (phpy)2 (μ-Cl)]2, and then evaluated as anticancer agents for the inhibition of the three proteolytic activities of human 20S proteasome, one of the main target for cancer therapy. These complexes were also screened for the inhibition of a couple of human cathepsins known to be involved in metastatic processes. A-C turned out to be active towards these enzymes. In addition, they showed in vitro antiproliferative activity against neuroblastoma SH-SY5Y, melanoma SK-Mel-28, hepatocellular adenocarcinoma HepG2 and colorectal adenocarcinoma Caco-2 tumor cell lines, without any sign of cytotoxicity in primary human fibroblasts WI-38. Moreover, these complexes induced apoptosis in the former tumor cell line, as displayed by cytofluorimetric analyses. This study indicated that these compounds may represent valuable lead structures for the development of new anticancer agents. © 2019 Elsevier B.V.
Aidi, M. ,
Keypour, H. ,
Shooshtari, A. ,
Bayat, M. ,
Hosseinzadeh, L. ,
Amiri rudbari, H. ,
Gable, R.W. Publication Date: 2019
Inorganica Chimica Acta (18733255) 490pp. 294-302
Here we report a number of novel macrocyclic Schiff base complexes with a homopiperazine skeleton. These symmetrical pentaaza macrocyclic Schiff base complexes were prepared via a template approach, based on the condensation reaction of an amine containing homopiperazine moiety and 2,6-diacetylpyridine or 2,6-pyridine dicarboxaldehyde in 1:1 mol ratio in the presence of Cd(II), Mn(II) and Zn(II) metal ions. These Schiff base complexes were characterized by elemental analyses, FT-IR, mass spectrometry and, in the cases of diamagnetic Zn(II) and Cd(II) complexes, 1H and 13C NMR spectroscopy. As well, the structures of [Mn(L1)(CH3OH)(ClO4)]ClO4 and [Cd(L2)(H2O)2](ClO4)2 have been determined by X-ray structural analyses, where the L1 and L2 are the products of the reaction of the new amine with 2,6–Pyridinedicarboxaldehyde or 2,6–diacetalpyridine, respectively. The coordination environment of the metal atoms in both of these complexes is best described as a distorted pentagonal bipyramid. The cytotoxic activities of these new complexes were also examined. The potency of complexes to induce cell death was screened on A2780, U37 MG, and H1299 cell lines, compared to doxorubicin which was used as a control. The results reveal that in some cases, the cytotoxic activity of complexes was stronger than that of doxorubicin as standard. Also, the bonding situation in the complexes, were analyzed by NBO and energy-decomposition analysis (EDA) and EDA-NOCV analysis. © 2018
Gholizadeh, M. ,
Pourayoubi, M. ,
Housaindokht, M.R. ,
Amiri rudbari, H. ,
Farimaneh, M. ,
Saneei, A. ,
Bruno, G. Publication Date: 2019
Turkish Journal Of Chemistry (13036130) 43(2)pp. 555-567
1,2-Ethylene-bis(para-methyl pyridinium) dichromate, (C 14 H 18 N 2) [Cr 2 O 7 ], is used as a new oxidizing agent in conversion of some alcohols to their corresponding carbonyl compounds in CH 3 CN solvent and also under solvent-free conditions. In both procedures, high conversion percentages are observed. However, a much shorter reaction time is achieved in solvent-free conditions. For allylic alcohols, the C = C bond is not oxidized and the examined saturated alcohol in this work (i.e. cyclo-hexanol) remains intact, which illustrates the mild nature of reagent used. The structure of the reagent is investigated by single-crystal X-ray diffraction analysis. The C–H · · · O and O · · · π interactions are the most important features of crystal packing, which are visualized by the Hirshfeld surface map. © TÜBİTAK
Adibi, H. ,
Abdolmaleki, S. ,
Shahabadi, N. ,
Golabi, A. ,
Mahdavi, M. ,
Zendehcheshm, S. ,
Ghadermazi, M. ,
Ansari, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2019
Polyhedron (02775387) 163pp. 20-32
The compound, [dmpH]2[pydc] (L) as ligand was synthesized by the proton-transfer reaction of pyridine-2,6-dicarboxylic acid (pydcH2) with 4-dimethylaminopyridine (dmap). The new coordination complexes of [dmpH]2[La2(pydc)4(H2O)4]·2H2O (1) and [dmpH]2[Ce(pydc)3]·2H2O (2) were prepared from the reaction of the ligand with La(NO3)3·6H2O and Ce(SO4)2·4H2O metal salts, respectively. All structures were characterized by X-ray crystallography. Cytotoxicity of compounds was tested under MTT method, against HT29 (a human colon adenocarcinoma), HepG2 (a human liver hepatocellular carcinoma) and HL60 (a human lymphocyte) cell lines. Complex (1) with IC50 values of about 1–100 μM was more active than other compounds on all three cell lines. The strongest anti-proliferative effect was observed for (1) toward HL60 cell line with IC50 value equal to 1 μM. High cytotoxicity of complexes indicated that they can be further evaluated for cancer treatment in the next set. UV–Vis absorption spectroscopy, emission titration and viscosity were employed to investigate the mode of interaction between (L), (1) and (2) with calf-thymus DNA. All studies represented that (L), (1) and (2) interact with CT-DNA via intercalation mode. A direct correlation was recognized between inhibitory and DNA interaction potent of the compounds. Also, the results of molecular docking were in agreement with obtained experimental data of DNA interaction. © 2019 Elsevier Ltd
Shafiee, B. ,
Duffield, J. ,
Timm, R. ,
Liyanage, R. ,
Lay, J.O. ,
Khosropour, A.R. ,
Amiri rudbari, H. ,
Beyzavi, M.H. Publication Date: 2019
Green Chemistry- England (14639262) 21(10)pp. 2656-2661
An eco-friendly, straightforward, and three-component condensation/cascade reaction of 4-hydroxycoumarins and (Z)-azlactones to construct diversified dihydro-5′H-spiro[benzo[c]chromene-8,4′-oxazole]-5′,6(7H)-diones as new masked amino acid derivatives has been developed with high to excellent yields and regio- A nd diastereoselectivity. This metal-free reaction proceeds via a one-pot cascade Michael addition/lactonization/decarboxylation reaction utilizing reusable propylene carbonate as a green solvent. The scale-up examination was also performed, showing high atom economy under the reaction conditions. Moreover, the mechanism of the reaction was further investigated using isotope-labeling, LC-MS monitoring, and TLC-MALDI-MS. © 2019 The Royal Society of Chemistry.
Zamani, P. ,
Phipps, J. ,
Hu, J. ,
Cheema, F. ,
Amiri rudbari, H. ,
Bordbar, A. ,
Khosropour, A.R. ,
Beyzavi, M.H. Publication Date: 2019
ACS Combinatorial Science (21568952) 21(8)pp. 557-561
A practical and efficient synthetic procedure to novel chromeno[3,2-d]oxazoles through a one-pot sequential multistep process is presented. This procedure proceeds efficiently in propylene carbonate (PC) as a green solvent and affords a wide range of the chromenooxazole scaffolds. © 2019 American Chemical Society.
Kazemi, Z. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Mirkhani, V. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. ,
Abbasi kajani, A. Publication Date: 2019
Polyhedron (02775387) 170pp. 70-85
A diastereomeric pair (homochiral and heterochiral) of Schiff base dioxo molybdenum complex was synthesized using chiral ligand (HL: R/S-1-((naphtalen-3-yl)methylenamino)propan-2-ol) in racemic form. Then, to separation of this diastereomeric pair, crystallization method was proposed which was successful with acetonitrile. 1H NMR technique was used to confirm the results. The complexes thoroughly characterized using FT-IR, elemental analysis, 1H NMR and 13C NMR techniques, and MoO2L(LH2)1 has been structurally characterized using single-crystal X-ray diffraction. The cytotoxic activity of the new compounds has been evaluated using MCF-7 (human breast adenocarcinoma) and HeLa (human cervix adenocarcinoma), in addition to normal human fibroblast cells using the MTT cytotoxicity assay. Compounds MoO2L(LH2)1 and MoO2L(LH2)2 revealed IC50 values 18 µM and 37 µM on MCF-7 and 58 µM and 17 µM on HeLa, respectively. MoO2L(LH2)2 showed high selectivity (3–13 folds) for cancerous cells over normal cells, as the maximum cell mortality of 8.77%. Furthermore, The HSA- and DNA-binding of the Mo(VI) complexes were investigated by absorption, emission spectroscopy, viscosity measurements and molecular docking. Their binding constant are calculated as: HSA-binding of MoO2L(LH2)1 is 6.7 × 104 M−1 and of MoO2L(LH2)2 is 5.8 × 104 M−1, while their DNA-binding are 5.6 × 104 M−1 and 2.2 × 105 M−1, respectively. Their thermodynamic parameters were also determined at different temperatures. © 2019 Elsevier Ltd
Askari, B. ,
Amiri rudbari, H. ,
Micale, N. ,
Schirmeister, T. ,
Efferth, T. ,
Seo, E. ,
Bruno, G. ,
Schwickert, K. Publication Date: 2019
Dalton Transactions (14779226) 48(42)pp. 15869-15887
Four Ru-Pd heterobimetallic complexes, each one in two different coordination modes (NNSS and NS) having metals connected by a binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N] [R = methyl, ethyl, n-butyl and isopropyl], were prepared by reacting the monochelate [(trinpropyl-phosphine)ClPd(HR2C2N2S2 κ-S,S-Pd)] with [(η6-p-cymene)RuCl2]2. Furthermore, two palladium homobimetallic complexes having two (trinpropyl-phosphine)ClPd moieties joined by a diethyldithiooxamidate in both κ-N,S Pd, κ-N′,S′ Pd′ and κ-N,N′ Pd, κ-S,S′ Pd′ coordination modes were synthesized. For both kinds of complexes, homo- A nd heterobimetallic, at room temperature and in chloroform solution, the NNSS coordination mode (kinetic compounds) turns out to be unstable and therefore the resulting complexes rearrange into a thermodynamically more stable form (NS coordination mode). The crystal structures of [(trinpropyl-phosphine)ClPd]2[μ-(ethyl)2-DTO κ-N,S Pd, κ-N′,S′ Pd′] (2) and [(η6-p-cymene)ClRu][μ-(methyl)2-DTO κ-N,S Ru, κ-N,S Pd] [(trinpropyl-phosphine)ClPd] (1c) were determined by solid state X-ray crystallography. Moreover, the higher stability of the thermodynamic species in the heterobimetallic complexes (Ru-Pd) was evaluated by means of computational studies in accordance with the maximum hardness principle. All stable NS complexes (i.e.1c-4c, 2 and the previously reported homobimetallic Ru complex 3) were tested against two leukemia cell lines, namely the drug-sensitive CCRF-CEM cell line and its multidrug-resistant sub-cell line CEM/ADR5000 showing anti-proliferative activity in the low micromolar range (∼1-5 μM) and micromolar range (∼10-25 μM), respectively. In addition, these complexes efficaciously block at least two out of the three proteolytic activities of the tumor target 20S proteasome, with heterobimetallic complex 3c and homobimetallic complex 3 possessing the best inhibitory profile. This journal is © The Royal Society of Chemistry.
Akbari, Z. ,
Rashidi ranjbar, Z. ,
Yousef ebrahimipour s., S.Y. ,
Amiri rudbari, H. ,
Lotfi, S. Publication Date: 2019
Main Group Chemistry (17451167) 18(2)pp. 89-100
In this paper, we report the synthesis, characterization and theoretical studies of two new cocrystals of 1,5 bis(3- pyridyl)-3,4-diaza-2,4-hexadiene (3-bpdh) with two simple organic acids; oxalic and succinic with 1:1 stoichiometric ratio. These cocrystals, [(3-bpdh)(oxalic acid)] (1) and [(3-bpdh)(succinic acid)] (2), have been prepared by slow evaporation of saturated solutions and characterized by elemental and thermal analysis, FTIR, 1H NMR spectroscopy, and single X-ray crystallography. X-ray crystal analyses show that these structures have been crystallized in triclinic and monoclinic space groups of P1 and P21/n, respectively. Also, the thermal behavior of compounds was investigated in an atmosphere of static air with thermal gravimetric analysis (TGA), differential thermal analysis (DTA). These structures have been studied theoretically using RB3LYP hybrid density functional method with 6-31G(d) basis set. DFT calculations have been used to predict the geometry of the cocrystal structures. Furthermore, molecular electrostatic potential (MESP) maps of the compounds have been generated. Theoretical results showgood agreement with the experimental data and these data show hydrogen bonding has played an important role in supramolecular structure formation. The cocrystal design was done based on the perfect selection of two distinct hydrogen donor and acceptor molecules. © 2019 - IOS Press and the authors. All rights reserved.
Publication Date: 2019
Transition Metal Chemistry (1572901X) 44(6)pp. 525-534
Four complexes of a new isothiosemicarbazone ligand have been prepared and characterized as μ2-pip-(NiL)2 (1), MnL2 (2), UO2L(BrSal)BuOH (3) and (μ2-MoO2L)2 (4) (H2L = 2-hydroxyacetophenone S-allyl isothiosemicarbazone.hydrobromide, BrSal = 5-bromosalicylaldehyde, pip = piperazine). All four complexes were characterized by X-ray crystallography, IR and elemental analyses. Complex 1 has a square planar coordination geometry in a binuclear arrangement such that both Ni atoms are coordinated to the phenolic-O, azomethine-N and thioamide-N atoms of L, and the bridging piperazine occupies the fourth position. For complex 2, the Mn atom connects to two N2O tridentate ligands in a distorted octahedron. The pentagonal bipyramidal geometry of complex 3 is provided by the tetradentate N2O2 ligand, n-butanol, and two oxo ligands around the uranium center. Finally, in the binuclear Mo complex (4), two N2O ligands coordinate to each molybdenyl center, together with the phenoxide-O donor of the adjacent molecule. © 2019, Springer Nature Switzerland AG.
Publication Date: 2019
Journal of Inorganic and Organometallic Polymers and Materials (15741443) 29(2)pp. 502-516
New discrete supramolecular coordination compound of Ni(II) namely (H 2 Lh)[Ni(pydc) 2 ]·5H 2 O (1), where pydc = pyridine-2,6-dicarboxylic acid and Lh = l-histidine has been fabricated and characterized by elemental analysis, spectral (IR, UV–Vis), thermal (TG/DTG) analysis and single crystal X-ray diffraction (XRD). The asymmetric unit of the title compound containing two halves of [Ni(pydc) 2 ] 2− anions, one (H 2 Lh) 2+ counter cation and five uncoordinated water molecules. The building units of this coordination compound connected via complicated strong and weak intermolecular interactions and made fascinating a 3D supramolecular architecture. In compound 1 two Ni1 II and Ni2 II ions are located at the center of distorted octahedrons. NiO nanoparticles were prepared using thermal decomposition of the (H 2 Lh)[Ni(pydc) 2 ]·5H 2 O complex at 450 °C and well characterized by Fourier transform infrared, XRD, scanning electron microscopy, and energy dispersive X-ray spectroscopy techniques, to examine the structure, morphology, particle size and phase composition. The XRD patterns proved that the nanosized NiO particles had high purity and crystallinity. So, the Ni(II) complex could be used as a good precursor for the fabrication of NiO nanoparticles as a result of its low temperature of decomposition. After that, this nanosize nickel oxide used as heterogeneous catalyst for the reduction of nitrophenols (NPs) in aqueous solution in the presence of excess NaBH 4 at room temperature. The reduction of 4-NP by NaBH 4 and catalyst has been extensively used as a model reaction for reduction of nitroarene, since it is easy to monitor with simple and fast UV–Vis technique, and there are no by-products. This reaction is also valuable in the view of green chemistry because 4-NP, one of the toxic materials in the wastewater, is transformed into a commercially important substance, 4-aminophenol (4-AP). NiO nanoparticles indicated excellent performance in the reduction of NP to corresponding AP within 21 min with rate constant about 0.15 min −1 . The effect of catalyst dosage also evaluated on the efficiency of reduction process. The NiO nanoparticles could be reused upon multipel cycles without changing in its structure and activity. © 2018, Springer Science+Business Media, LLC, part of Springer Nature.
Askari, B. ,
Amiri rudbari, H. ,
Micale, N. ,
Schirmeister, T. ,
Giannetto, A. ,
Lanza, S. ,
Bruno, G. ,
Mirkhani, V. Publication Date: 2019
Polyhedron (02775387) 164pp. 195-201
Addition of H2R2DTO (R = {S}-1-phenylethyl and DTO = dithiooxamide) to the bis(benzonitrile)palladium(II) chloride complex in chloroform afforded the mononuclear Pd(DTO)2·2HCl complex. The complex treated with NaHCO3 for removing of HCl and then reacted with [Pd(ƞ3-allyl)(µ-Cl)]2 for preparation of a new trimetallic organopalladium(II) complex. The molecular structure of the trimetallic complex was determined by X-ray diffraction indicating a planar geometry around each palladium center. Also, variable temperature spectroscopy for this complex was performed in CDCl3 in the range 298–390 K, and simulations of the dynamic spectra were performed using the gNMR program. A comparison between the target-based activity of the Pd(II) complex and its trinuclear heterobimetallic platinum(II) analogue as potential anticancer agents was also conducted. All the biological tests showed that both Pd(II) and Pt(II) complexes can fairly inhibit cathepsin B (Cat-B) and cathepsin L (Cat-L) as well as two out of three activities of 20S proteasome. © 2019 Elsevier Ltd
Abdolmaleki, S. ,
Yarmohammadi, N. ,
Adibi, H. ,
Ghadermazi, M. ,
Ashengroph, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2019
Polyhedron (02775387) 159pp. 239-250
Proton-transfer compounds were prepared by the reaction of pyridine-2,6-dicarboxylic acid (pydcH2) with 1-methylimidazole (1-mim) and 2-methyimidazole (2-mim) in 1:2 molar ratio. The reaction of ligands with antimony(III)chloride led to complexes formulated as [Sb(pydcH)(pydc)(H2O)] (1) and [Sb2(pydcH)2(H2O)2(Cl)2(OH)]2·2H2O (2). Both two of complexes were characterized by elemental analysis, IR, UV–Vis and NMR spectroscopy and also their structures were confirmed by X-ray crystallography. Cyclic voltammetry measurements on the complexes revealed one redox couple corresponding to Sb(III)/Sb(V) at E0′ of −0.184 to −0.052 V versus Ag/AgCl, under argon. Aeration proved the further interaction potent of complex (2) with oxygen compared to (1), within 5 min. In this study, the cytotoxic potential of each of three compounds were evaluated, using oxaliplatin as a standard, under MTT method, against MCF7 (a human breast cancer), H1299 (a human non-small cell lung carcinoma), HT29 (a human colon adenocarcinoma), HepG2 (a human liver hepatocellular carcinoma) and βTC (a mouse beta pancreatic) cell lines. Complex (2) with E0′ about three and a half times (1) exhibited more significant toxicity compared to (1). The strongest cytotoxic effect for (2) was indicated on HepG2 cell line (IC50 = 1 μM). Antibacterial activity of the compounds was evaluated against three Gram-positive bacteria namely Staphylococcus aureus, Streptococcus pyogenes and Enterococcus faecalis and also three Gram-negative bacteria namely Escherichia coli, Pseudomonas aeruginosa and Proteus vulgaris through the established antibacterial assays including broth microdilution method using 2,3,5-triphenyl tetrazolium chloride (TTC, as chromogenic marker) and agar well diffusion method. Both two complexes showed an enhanced antibacterial activity in comparison with the standard drug chloramphenicol. © 2018
Publication Date: 2018
Polyhedron (02775387) 155pp. 114-128
Although numerous Schiff base complexes have been synthesized and characterized, reports on Schiff base ligands and complexes derived from amines containing terminal allyl group are rare. In this work, four halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes (3,5-dichlorosalicylaldehyde, 3,5-dibromosalicylaldehyde, 3,5-diiodosalicylaldehyde and 3-bromo-5-chlorosalicylaldehyde) with allyl amine in water as green solvent at ambient temperature and characterized by elemental analyses, NMR (1H and 13C), and FT-IR spectroscopy. In continue, their Cu(II) complexes were synthesized and characterized by elemental analyses, FT-IR and single-crystal X-ray diffraction. All complexes show halogen-halogen, π–π CH–π interactions and also metal–halogen secondary bonds in crystal packing. The coordination geometry around the Cu(II) in all reported compounds is best described as square planar with two axially elongated interactions named metal–halogen secondary bond (Cu…X), all beyond the sum of the corresponding vdW radii (3.421 Å for Cu…Cl in (Cl2L)2Cu, 3.463 Å for Cu…Br in (Br2L)2Cu, 3.486 Å for Cu…I in (I2L)2Cu and 3.467 Å for Cu…Cl in (BrClL)2Cu). The crystal structures have also been subjected to Hirshfeld surface analysis which reveals that approximately most of the close contacts correspond to relatively weak interactions. Also, all of the interactions in crystal packing have been analyzed by theoretical calculations. © 2018 Elsevier Ltd
Ariyaeifar, M. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Kazemi, Z. ,
Abbasi kajani, A. ,
Zali boeini, H. ,
Kordestani, N. ,
Bruno, G. ,
Gharaghani, S. Publication Date: 2018
Journal of Molecular Structure (00222860) 1161pp. 497-511
Eight enantiomerically pure halogenated Schiff base compounds were synthesized by reaction of halogenated salicylaldehydes with 3-Amino-1,2-propanediol (R or S) in water as green solvent at ambient temperature. All compounds were characterized by elemental analyses, NMR (1H and 13C), circular dichroism (CD) and FT-IR spectroscopy. FS-DNA binding studies of these compounds carried out by fluorescence quenching and UV–vis spectroscopy. The obtained results revealed that the ligands bind to DNA as: (R–ClBr) > (R–Cl2) > (R–Br2) > (R–I2) and (S–ClBr) > (S–Cl2) > (S–Br2) > (S–I2), indicating the effect of halogen on binding constant. In addition, DNA-binding constant of the S– and R-enantiomers are different from each other. The ligands can form halogen bonds with DNA that were confirmed by molecular docking. This method was also measured the bond distances and bond angles. The study of obtained data can have concluded that binding affinity of the ligands to DNA depends on strength of halogen bonds. The potential anticancer activity of ligands were also evaluated on MCF-7 and HeLa cancer cell lines by using MTT assay. The results showed that the anticancer activity and FS-DNA interaction is significantly dependent on the stereoisomers of Schiff base compounds as R-enantiomers displayed significantly higher activity than S-enantiomers. The molecular docking was also used to illustrate the specific DNA-binding of synthesized compounds and groove binding mode of DNA interaction was proposed for them. In addition, molecular docking results indicated that there are three types of bonds (H– and X-bond and hX-bond) between synthesized compounds and base pairs of DNA. © 2018 Elsevier B.V.
Publication Date: 2018
Journal of Structural Chemistry (00224766) 59(5)pp. 1176-1180
New end-on azido-bridged dinuclear copper(II) complex [Cu2L2(μ1,1-N3)2] (I) (HL = 2-[(3-amino-2,2-dimethylpropylimino)-methyl]-4-bromophenol) is synthesized and characterized by the elemental analysis and FT-IR spectroscopy. The crystal structure of I is determined by X-ray diffraction. The crystal of I is monoclinic, space group P21/c, a = 10.7926(4) Å, b = 12.4222(4) Å, c = 11.0894(4) Å, β = 100.085(2)°, V = 1463.76(9) Å3, Z = 2. The crystal structure shows that the structure contains [Cu2L2(μ1,1-N3)2] units joined together by intermolecular H-bonding interactions to form a 2D rectangular grid. © 2018, Pleiades Publishing, Ltd.
Publication Date: 2018
ACS Combinatorial Science (21568952) 20(6)pp. 358-365
A versatile and straightforward synthetic strategy for the construction of new tetrasubstituted 1,3-diazinones is described. The procedure is based on CsF-catalyzed, microwave-assisted, ring transformation reaction of arylidene azlactones with amidines. Moreover, this technique provides diversified trans-N-(6-oxo-1,4,5,6-tetrahydropyrimidin-5-yl)benzamides with a good antimicrobial activity. © 2018 American Chemical Society.
Publication Date: 2018
Journal Of Biological Inorganic Chemistry (09498257) 23(2)pp. 181-192
The interaction of three complexes [Zn(II), Cu(II), and V(IV)] derived from an asymmetric bidentate Schiff-base ligand with DNA and HSA was studied using fluorescence quenching, UV–Vis spectroscopy, viscosity measurements, and computational methods [molecular docking and our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM)]. The obtained results revealed that the DNA and HSA affinities for binding of the synthesized compounds follow as V(IV) > Zn(II) > Cu(II) and Zn(II) > V(IV) > Cu(II), respectively. The distance between these compounds and HSA was obtained based on the Förster’s theory of non-radiative energy transfer. Furthermore, computational molecular docking was carried out to investigate the DNA- and HSA-binding pose of the compounds. Molecular docking calculations showed that H-bond, hydrophobic, and π-cation interactions have dominant role in stability of the compound–HSA complexes. ONIOM method was utilized to investigate the HSA binding of the compounds more precisely in which molecular-mechanics method (UFF) and semi-empirical method (PM6) were selected for the low layer and the high layer, respectively. The results show that the structural parameters of the compounds changed along with binding, indicating the strong interaction between the compounds with HSA and DNA. Viscosity measurements as well as computational docking data suggest that all metal complexes interact with DNA, presumably by groove-binding mechanism. © 2017, SBIC.
Dehkhodaei, M. ,
Sahihi, M. ,
Amiri rudbari, H. ,
Ariaeefar, M. ,
Gharaghani, S. ,
Azadbakht, R. ,
Taheri, S. ,
Abbasi kajani, A. Publication Date: 2018
Journal of Molecular Liquids (18733166) 264pp. 386-397
As for daily increasing mortality rate in world due to the growth of cancer causing agents, design and synthesis of new compounds with anticancer potential benefits is one of the most important challenges for researchers. In the present work, we synthesized a new Schiff base Pd(II) complex in bulk-scale and also in nano-scales by Sonochemical method. The structure of synthesized complex was determined by single crystal X-ray diffraction technique. Then the cell viability percent of HeLa cancer cells was studied by MTT assay. The results confirmed that reducing the size has salient effect in annihilation of cancer cells. Also, nano-scale complex reached to IC50 in 10 μM of concentration. Binding ability of the nano- and bulk-scale Pd(II) Schiff base complex with calf thymus DNA and human serum albumin was investigated using combination of experimental (fluorescence, circular dichroism (CD) and viscosity) and computational (molecular docking, molecular dynamics simulation and QM/MM) methods. The estimated binding constants for the complex in both of bulk- and nano-scales showed that the nano-scale complex binds more tightly to DNA than its bulk-scale form. This finding is in good agreement with MTT assay results. Molecular docking studies revealed that Pd(II) complex binds to the minor groove and IB binding site of DNA and HSA, respectively. Also, MD simulation studies showed that complexation with the Pd(II) complex changes the structure of HSA with compared to free protein. Finally, the ONIOM results indicated that the structural parameters of the compound changed along with binding to DNA and HSA, indicating the strong interaction between the compound and these biomacromolecules. The values of binding constants depend on the extent of the resultant changes. © 2018
Torabi, V. ,
Kargar, H. ,
Akbari, A. ,
Behjatmanesh-ardakani, R. ,
Amiri rudbari, H. ,
Tahir, M.N. Publication Date: 2018
Journal of Coordination Chemistry (10290389) 71(22)pp. 3748-3762
A new asymmetric tetradentate Schiff base, bis(5-methoxysalicylidene)-4-methylbenzene-1,2-diamine), H 2 L, and its Ni(II) complex were prepared and characterized using elemental analyses (CHN), FTIR, UV–Vis, 1 H NMR, and 13 C{ 1 H} NMR spectroscopic techniques, and crystal structures of both were determined by X-ray crystallography. For both ligand and Ni(II) complex, density functional theory calculations to find geometry parameters, IR frequencies, electronic properties, and natural bond orbital analysis (NBO) were done with M062X method and Def2-TZVP basis set. All calculated data are consistent with the experiments. NBO data for the Ni(II) complex show that the main type of transition in UV-Vis is interligand charge-transfer, which is assigned as π-π*. © 2018, © 2018 Informa UK Limited, trading as Taylor & Francis Group.
Publication Date: 2018
Journal of Biomolecular Structure and Dynamics (07391102) 36(12)pp. 3130-3136
Jamshidvand, A. ,
Sahihi, M. ,
Mirkhani, V. ,
Moghadam, M. ,
Mohammadpoor baltork, I. ,
Tangestaninejad, S. ,
Amiri rudbari, H. ,
Kargar, H. ,
Keshavarzi, R. ,
Gharaghani, S. Publication Date: 2018
Journal of Molecular Liquids (18733166) 253pp. 61-71
In this work, five new Schiff base ligands were synthesized and characterized by 1H NMR, 13C NMR, FT-IR, UV–Vis and elemental analysis (CHN). L1, L2 and L3, were derived from condensation of 2-Hydroxy-5-bromobenzaldehyde with 4-aminobenzoic acid, 3-aminobenzoic acid and 3-amino-4-methylbenzoic acid with 1:1 M ratio, respectively. While, L4 and L5 were prepared from condensation of 4-aminobenzoate with 3-ethoxy-2-hydroxybenzaldehyde and 3-methoxy-2-hydroxybenzaldehyd with 1:1 M ratio, respectively. Furthermore, the crystal structure of L4 and L5 were determined by single crystal X-ray analysis. The interaction of Schiff base ligands with fish sperm DNA (FS-DNA) was investigated under physiological conditions using fluorescence quenching, UV–Vis spectroscopy, molecular docking and molecular dynamics (MD) simulation methods. The estimated binding constants (kb) for the DNA-Ligands complexes were 8.9 × 104 M−1, 6.8 × 104 M−1, 1.2 × 105 M−1, 2.3 × 105 M−1, 1.7 × 105 M−1 for L1, L2, L3, L4 and L5, respectively. Based on similarity of the ligands structures and their Kb values, their affinity for binding to FS-DNA follow as: L3 > L1 > L2 and L4 > L5. The results revealed that ligands with stronger electron donating substituents, have higher DNA-binding ability than the others. Also, molecular docking results show that all of the synthesized ligands are minor groove binders and H-bond interactions have dominant role in the stability of ligand-DNA complexes. © 2018 Elsevier B.V.
Rajabi-salek, M. ,
Zolfigol, M.A. ,
Zarei, M. ,
Noroozizadeh, E. ,
Mohammadpoor baltork, I. ,
Amiri rudbari, H. Publication Date: 2018
ChemistrySelect (23656549) 3(45)pp. 12791-12796
Herein, a convenient method for the synthesis of bis-naphthodipyrans from the condensation of naphthalene-2,3-diol, malononitrile and various aromatic aldehydes using acetic acid functionalized pyridinium salt 1-(carboxymethyl)pyridinium bromide [CMPy]Br as a novel, efficient, reusable and nanocatalyst is described. The synthesized catalyst was fully characterized by using various techniques such as single crystal X-ray diffraction (SCXRD), 1H NMR, 13C NMR, Fourier transform infrared spectroscopy (FT-IR), mass spectra, scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD) and Differential thermal analysis (TG/DTG). The major advantages of the convenient method are high yields, short reaction time, and reusability of the catalyst. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Publication Date: 2017
Acta crystallographica. Section C, Structural chemistry (20532296) 73(8)pp. 609-612
The title Schiff base compound {systematic name: 2-[5-[(E)-(2-hydroxybenzylidene)amino]-4-(2-{5-[(E)-(2-hydroxybenzylidene)amino]-2-(2-hydroxyphenyl)-1,3-thiazol-4-yl}disulfanyl)-1,3-thiazol-2-yl]phenol}, C32H22N4O4S4, incorporating a disulfanediyl (dithio) linkage, was obtained from the condensation reaction between two equivalents of salicylaldehyde and one equivalent of dithiooxamide in dimethylformamide, and was characterized by elemental analysis, IR spectroscopic analysis and single-crystal X-ray diffraction. A one-dimensional chain is formed along the b axis via double intermolecular C-H⋯S hydrogen bonds. The HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energies and some related molecular parameters were calculated at the B3LYP/6-311G(d,p) level of theory. The molecular hyperpolarizability was also calculated. © 2017 International Union of Crystallography.
Publication Date: 2017
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy (13861425) 178pp. 198-202
A new isoindoline–based highly efficient turn-on fluorescent chemodosimeter S with a thioamide functionality as a binding site for selective detection of Hg2 + ion has been developed. The chemodosimeter S showed an extreme selectivity for detection of Hg2 + ion among various two and three-valent metal ions in acetonitrile/water (70/30, v/v). It was found that, in the presence of Hg2 + ion the non-fluorescent chemodosimeter S was efficiently and rapidly desulfurized to the corresponding highly fluorescent amide 1. A good linear relationship was shown between the fluorescence intensity and the concentration of Hg2 + within the range of 0–1 μM, with a detection limit of 2.03 × 10− 8 M. © 2017 Elsevier B.V.
Publication Date: 2017
New Journal of Chemistry (11440546) 41(20)pp. 12198-12204
A new asymmetric macrocyclic ligand was synthesized and characterized by NMR studies, X-ray diffraction and mass spectroscopy. Based on the photoinduced electron transfer (PET) fluorescence enhancement mechanism, the ligand has been successfully used for the efficient detection of Pb2+ in aqueous buffer media (pH 7.4). The detection limit of Pb2+ is up to 9.63 × 10-10 M. © 2017 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
Publication Date: 2017
Journal of Macromolecular Science, Part B: Physics (1525609X) 56(9)pp. 655-669
The interaction of an asymmetric Schiff base ligand derived from allylamine and 2,3-dihydroxybenzaldehyde and its molybdenum (VI) complex with deoxyribonucleic acid (DNA) and bovine serum albumin (BSA) were studied using spectroscopic and molecular docking methods. The spectroscopic results revealed that the DNA and BSA affinity for binding the Mo(VI) complex is greater than its ligand. Furthermore, the molecular docking calculations showed that H-bond, hydrophobic, π-π and π-cation interactions had the dominant roles in the stability of the compound-BSA complexes. The DNA interaction results suggested that the compounds interacted with DNA by the groove binding mechanism. © 2017 Taylor & Francis Group, LLC.
Keivanloo, A. ,
Soozani, A. ,
Bakherad, M. ,
Mirzaee, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2017
Tetrahedron (14645416) 73(12)pp. 1633-1639
1,2,4-trisubstituted pyrrolo[1,2-a]quinoxalines are synthesized through the multi-component reaction of 3-substituted 2-chloroquinoxalines, propargyl bromide, and excess secondary amines in the presence of a palladium copper catalytic system. This one-pot process provides an unexpected synthesis of new trisubstituted pyrrolo[1,2-a]quinoxalines by the introduction of two amine substituents onto the fused pyrrole rings in a single reaction procedure. The compounds formed are fully characterized by the analytical spectral data and X-ray analysis. A number of synthesized pyrrolo[1,2-a]quinoxaline derivatives are also screened against the three bacterial strains Micrococcus luteus, Pseudomonas aeruginos, and Bacillus subtilis. According to the results obtained, compounds 3b, 3c, and 3e are active against M. luteus, compounds 3b and 3e are active against Ps. Aeruginos, and only compound 3f is active against all the three bacterial strains. © 2017 Elsevier Ltd
Publication Date: 2017
Computational and Theoretical Chemistry (2210271X) 1099pp. 75-86
Quantum chemical calculations based on density functional theory (DFT) and X-ray crystal structure analysis of some ethyl 4-aryl-6-methyl-2-oxo-1,2,3,4-tetrahydropyridine-5-carboxylates (THPYs) were applied in order to elucidate the effect of variations of the additional substituent on the C4-aryl ring on the molecular geometry, conformation and packing of molecules in the crystalline lattice. Due to the presence of the C4 stereocenter, these compounds exist as a racemic mixture in the crystal structure. Intermolecular interactions between the potential hydrogen donor (N[sbnd]H) and hydrogen acceptor (2-CO) of the heterocycle in the enantiomeric pair forming a sheet like dimeric structure, which provides especial stability to the crystal packing. The existence of the short intramolecular interactions (C[sbnd]H⋯π) and (C[sbnd]H⋯O) are a key feature which imparts also additional stability to the molecular conformation in the solid state. Most computational data including conformation of the heterocycle, the values of the bond lengths and angles are well in agreement with the experimental data. Ring flip calculations for 4-phenyl substituent explain the extreme torsional strain caused by the eclipsing of the carbon-hydrogen bonds in 3-CH2 moiety with the neighboring C4[sbnd]Caryl and C4[sbnd]H bonds and also the changes of some characteristic bond lengths and angles. These calculations indicate the more favored pseudo-axial orientation of the phenyl group over the pseudo-equatorial orientation. © 2016 Elsevier B.V.
Asadi, B. ,
Landrani, A. ,
Mohammadpoor baltork, I. ,
Tangestaninejad, S. ,
Moghadam, M. ,
Mirkhani, V. ,
Amiri rudbari, H. Publication Date: 2017
ACS Combinatorial Science (21568952) 19(6)pp. 356-364
Unsymmetrical 1,2,5,6-tetrahydropyridine-3-carboxylates were obtained for the first time from a five-component Fe3O4@TDSN-Bi(III)-catalyzed reaction of aryl aldehydes, aryl amines, and ethyl acetoacetate. This magnetically separable catalyst enabled the selective incorporation of two different aryl amines or two different aryl aldehydes into the product, and provided excellent yields, short reaction times, mild reaction conditions, satisfactory catalyst recyclability, and low catalyst loading. © 2017 American Chemical Society.
Piri, A. ,
Molaei, F. ,
Hashemi, L. ,
Morsali, A. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2017
Journal Of The Iranian Chemical Society (1735207X) 14(7)pp. 1541-1548
Assembly of quinoxaline with Cd(II) in the presence of SCN− anion produces a new coordination polymer [Cd(Quinoxaline)(SCN)2(CH3CN)]n[Cd(Quinoxaline)2(SCN)2]n (1) and is characterized by IR, 1H NMR and 13C NMR spectroscopy. The single-crystal X-ray data of compound 1 show that this coordination polymer grows in two-dimensional supramolecular structure. In this polymer, the organic ligand chelate through its one nitrogen atom to cadmium(II) atom and thiocyanate anion acts as a bridge to two cadmium(II) atom in the chains. Also, nanoscale of CdS has been synthesized by calcination at 400, 500 and 600 °C under air atmosphere and characterized by scanning electron microscopy, X-ray powder diffraction and energy-dispersive X-ray. The thermal stability of compound 1 was studied by thermal gravimetric and differential thermal analyses. © 2017, Iranian Chemical Society.
Asadi, B. ,
Landrani, A. ,
Mohammadpoor baltork, I. ,
Tangestaninejad, S. ,
Moghadam, M. ,
Mirkhani, V. ,
Amiri rudbari, H. Publication Date: 2017
Tetrahedron Letters (00404039) 58(1)pp. 71-74
Fe3O4-TDSN-Bi(III) was utilized as an efficient and reusable catalyst for the regioselective one-pot synthesis of quinoline derivatives from arylamines, arylaldehydes and methyl propiolate under microwave irradiation and solvent-free conditions. Also, bis-quinolines were obtained in high yields from dialdehydes or diamines. Atom-economy, high to excellent yields, easy work-up, as well as simple catalyst recovery and reusability are the key features of this procedure. © 2016 Elsevier Ltd
Kazemi, Z. ,
Amiri rudbari, H. ,
Mirkhani, V. ,
Sahihi, M. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. ,
Abbasi kajani, A. ,
Azimi gandomani, G. Publication Date: 2017
European Journal of Medicinal Chemistry (02235234) 135pp. 230-240
The reaction of a racemic mixture of Schiff base tridentate ligand with vanadium(V) affords homochiral vanadium complex, (VO(R-L))2O and (VO(S-L))2O due to ligand “self-recognition” process. The formation of homochiral vanadium complex was confirmed by 1H NMR, 13C NMR and X-ray diffraction. The HSA- and DNA-binding of the resultant complex is assessed by absorption, fluorescence and circular dichroism (CD) spectroscopy methods. Based on the results, the HSA- and DNA-binding constant, Kb, were found to be 8.0 × 104 and 1.9 × 105 M−1, respectively. Interestingly, in vitro cytotoxicity assay revealed the potent anticancer activity of this complex on two prevalent cancer cell lines of MCF-7 (IC50 value of 14 μM) and HeLa (IC50 value of 36 μM), with considerably low toxicity on normal human fibroblast cells. The maximum cell mortality of 12.3% obtained after 48 h incubation of fibroblast cells with 100 μM of the complex. Additionally, the specific DNA- and HSA-binding was also shown using molecular docking method. The synthesized complex displayed high potential for biomedical applications especially for development of novel and efficient anticancer agents. © 2017 Elsevier Masson SAS
Beheshti, A. ,
Nozarian, K. ,
Babadi, S.S. ,
Noorizadeh, S. ,
Motamedi, H. ,
Mayer, P. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2017
Journal of Solid State Chemistry (1095726X) 249pp. 70-79
Two new compounds namely [Cu(SCN)(µ-L)]n (1) and {[Ag (µ2-L)](ClO4)}n (2) have been synthesized at room temperature by one-pot reactions between the 1,1-(1,4-butanediyl)bis(1,3-dihydro-3-methyl-1H-imidazole- 2-thione) (L) and appropriate copper(I) and silver(I) salts. These polymers have been characterized by single crystal X-ray diffraction, XRPD, TGA, elemental analysis, infrared spectroscopy, antibacterial activity and scanning probe microscopy studies. In the crystal structure of 1, copper atoms have a distorted trigonal planar geometry with a CuS2N coordination environment. Each of the ligands in the structure of 1 acting as a bidentate S-bridging ligand to form a 1D chain structure. Additionally, the adjacent 1D chains are interconnected by the intermolecular C-H…S interactions to create a 2D network structure. In contrast to 1, in the cationic 3D structure of 2 each of the silver atoms exhibits an AgS4 tetrahedral geometry with 4-membered Ag2S2 rings. In the structure of 2, the flexible ligand adopts two different conformations; gauche-anti-gauche and anti-anti-anti. The antibacterial studies of these polymers showed that polymer 2 is more potent antibacterial agent than 1. Scanning probe microscopy (SPM) study of the treated bacteria was carried out to investigate the structural changes cause by the interactions between the polymers and target bacteria. Theoretical study of polymer 1 investigated by the DFT calculations indicates that observed transitions at 266 nm and 302 nm in the UV–vis spectrum could be attributed to the π→π* and MLCT transitions, respectively. © 2016 Elsevier Inc.
Dehkhodaei, M. ,
Sahihi, M. ,
Amiri rudbari, H. ,
Gharaghani, S. ,
Azadbakht, R. ,
Taheri, S. ,
Abbasi kajani, A. Publication Date: 2017
Journal of Molecular Liquids (18733166) 248pp. 24-35
Herein, we synthesized a new nano-scale Schiff base Ni(II) complex in water as a green solvent and at ambient temperature. The compound was characterized using FT-IR and elemental analysis. Also, its molecular structure was determined by single crystal X-ray diffraction technique. The MTT assay results indicated that the anticancer activity of the compound is affected by its size. Finally, binding ability of the nano-scale Ni(II) Schiff base complex with calf thymus DNA and human serum albumin was investigated using combination of experimental (UV–Vis, fluorescence, circular dichroism (CD) and viscosity) and computational (molecular docking, molecular dynamics simulation and qm/mm) methods. The estimated binding constants for the DNA-complex and HSA-complex were about 104 M− 1. Molecular docking studies revealed the binding of Ni(II) complex to the minor groove of DNA and warfarin binding site of protein by formation of hydrogen bond, π-cation and hydrophobic interactions. MD simulation studies revealed that complexation with NiL2 changed the structure of HSA when compared to free protein. Finally, the ONIOM results showed that the structural parameters of the compound changed along with binding to DNA and HSA, indicating the strong interaction between the compound and these biomacromolecules. © 2017 Elsevier B.V.
Dehkhodaei, M. ,
Khorshidifard, M. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Azimi gandomani, G. ,
Habibi, N. ,
Taheri, S. ,
Bruno, G. ,
Azadbakht, R. Publication Date: 2017
Inorganica Chimica Acta (18733255) 466pp. 48-60
Four new Schiff base complexes (NiL2, CoL2, CuL2 and ZnL2) (HL: ((E)-2-((isopropylamino) methyl) phenol) were synthesized and characterized by CHN elemental analysis, FT-IR and single crystal X-ray diffraction technique. The crystallographic data reveal that in all complexes the metal centers are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two moles of Schiff base ligand HL and geometry around the metal center in all of them is distorted tetrahedral. In addition, 1H and 13C NMR techniques were employed for characterization of diamagnetic ZnL2 complex. The binding affinity of complexes with DNA (fish sperm DNA, FS-DNA) and Human Serum Albumin (HSA) were investigated using fluorescence quenching, chemometrics, UV–Vis spectroscopy, viscosity measurements and molecular docking methods. The obtained results revealed that the DNA and HSA affinity for binding to complexes are in the following order: CuL2 > ZnL2 > CoL2 > NiL2 and NiL2 > ZnL2 > CuL2 > CoL2. The distance between complexes and HSA was obtained based on the Förster's theory of non-radiative energy transfer. The computational molecular docking results showed that H-bond interactions, hydrophobic interactions, π-π stacking and π-cation interactions have dominant role in the stability of HSA-ML2 (M: Cu, Co, Ni and Zn). The computational docking and viscosity results suggest that all metal complexes interact with DNA presumably by the groove binding mechanism. © 2017 Elsevier B.V.
Publication Date: 2017
Journal of Macromolecular Science, Part B: Physics (1525609X) 56(9)pp. 636-643
The interaction of a new heterocyclic Schiff base bearing pyridine and pyrimidine cycles, with human serum albumin (HSA) using molecular docking and molecular dynamics simulation methods was examined. Molecular docking studies showed that the ligand was bonded to the IB domain of the protein. It was found that there was one hydrogen bond interaction between HSA and the ligand. The standard Gibbs free energy for binding of the ligand to HSA was calculated as −9.63 kcal.mol−1. The results of the molecular dynamics simulation showed that the root mean square deviation (RMSD) of the non-liganded HSA and the HSA–ligand complex reached equilibration after 1000 ps. The study of the radius of gyration revealed that there was a conformational change when the HSA–ligand complex was formed. Finally, analyzing the RMS fluctuations (RMSF) suggested that the structure of the ligand binding site remained approximately rigid during the simulation. © 2017 Taylor & Francis Group, LLC.
Publication Date: 2017
Tetrahedron (14645416) 73(11)pp. 1397-1406
1-Azabicyclo[3.3.0]oct-3-en-2-one derivatives were synthesized efficiently through the facile cascade reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with arylidene azlactones. This research provides a straightforward procedure for the synthesis of a novel class of multicyclic semi-alkaloids which shows good antimicrobial activity. Under catalyst-free, mild, and solventless condition, a wide range of fused tricyclic derivatives was obtained in high yields. © 2017 Elsevier Ltd
Publication Date: 2016
Journal of Organometallic Chemistry (0022328X) 825pp. 25-32
Three organotin(IV) complexes, Ph4Sn2L (1), Me2Sn(H2L) (2) and Bu2Sn(H2L) (3) have been formed from reaction of R2SnCl2(R = Ph, Me and Bu) with a multiprotic dihydrazone, 1,5-bis((2-hydroxynaphthaldehyde) thiocarbohydrazone (H4L). The synthesized compounds have been investigated by elemental analysis, IR,1H NMR, and119Sn NMR spectroscopy. The structure of 1 has been also confirmed by X-ray crystallography. The results show 1 is binuclear and fully deprotonated thiocarbohydrazone supplies two different tridentate dianionic domains, NNO and ONS, for coordination to two diphenyltin(IV) moieties. Coordination number of both tin(IV) center is five and it is maintain in solution. In 1 and 2 only one part of ligand as doubly deprotonated ONS donor was coordinated with tin and a mononuclear organotin complex with coordination number of five was formed. The in vitro antibacterial activity of ligand and complexes has been evaluated against Gram-positive (B. subtilis and S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria and compared with standard drugs. The synthesized compounds also have been investigated for the chromosomal and plasmid DNA cleavage activity. All complexes significantly inhibited bacterial growth and completely degrade the treated DNA. © 2016 Elsevier B.V.
Publication Date: 2016
Journal of Molecular Structure (00222860) 1103pp. 94-102
A new bidentate ON Schiff base ligand, HL, was synthesized by simple condensation reaction of isopropylamine and salicylaldehyde. Then by reaction of HL and VO(acac)2 in the ratio of 2:1 at ambient temperature, a new oxovanadium(IV) Schiff base complex, VOL2, was synthesized. The Schiff base ligand and its oxovanadium(IV) complex were characterized by elemental analyses, FT-IR, 1H NMR, 13C NMR and UV-visible spectroscopies. The crystal structure of oxovanadium(IV) complex, VOL2, was also determined by single crystal X-ray analysis. The vanadium center in this structure is coordinated to two bidentate Schiff base ligands with the two nitrogen and two phenolate oxygen atoms in equatorial positions and one oxo oxygen in the axial position to complete the distorted trigonal bipyramidal N2O3 coordination sphere. Catalytic performance of the VOL2 complex was studied in the selective oxidation of thioanisole with the green oxidant 35% aqueous H2O2 under solvent-free conditions and under organic solvents (EtOH, CHCl3, CH2Cl2, DMF, CH3CN, EtOAc) as a model. Due to better catalytic performance of the VOL2 complex under solvent-free conditions, this complex used for the oxidation of the different sulfides to the corresponding sulfones under solvent-free conditions. The use of hydrogen peroxide as oxidant and the absence of solvent makes these reactions interesting from environmental and economic points of view. © 2015 Elsevier B.V. All rights reserved.
Esteghamat-panah, R. ,
Farrokhpour h., H. ,
Hadadzadeh h., H. ,
Abyar, F. ,
Amiri rudbari, H. Publication Date: 2016
RSC Advances (20462069) 6(28)pp. 23913-23929
The interaction of a new cyclometallated Rh(iii) complex, [Rh(phpy-κ2N,C2′)2(dafone)]+ (phpy-κ2N,C2′ = pyridine-2-yl-2-phenyl and dafone = 4,5-diazafluoren-9-one), with DNA and BSA was investigated. The in vitro cytotoxicity tests of the complex against three cancer cell lines demonstrate that the complex can be introduced as an efficient anticancer agent. The binding of the complex to DNA and BSA was modeled by molecular docking. The three-layer ONIOM method (QM:QM:MM) was employed to calculate the interaction energy between DNA and the complex, where QM and MM are abbreviations of quantum mechanics and molecular mechanics, respectively. The complex and a part of the DNA were considered in the QM region at the same theoretical level, whereas the different basis sets for DNA, the complex, and the rest of system were considered in the MM region. Density functional theory (DFT) employing the M062X functional was used for the QM parts of the system. The M062X functional is one the best DFT functionals, introduced in recent years, which considers non-covalent interactions properly. The UV spectra of the complex interacting with DNA in the gas phase and water were calculated using the two- and three-layer ONIOM methods employing time-dependent density functional theory (TD-DFT) to investigate the effect of the interaction on the electronic structure of the complex. The calculations interestingly confirm the variations observed in the recorded spectra of the complex due to its interaction with DNA. © The Royal Society of Chemistry 2016.
Publication Date: 2016
Australian Journal of Chemistry (14450038) 69(8)pp. 872-880
Various 4,6-diaryl substituted 2-oxo-1,2,3,4-tetrahydropyrimidines (THPMs) were oxidized to 2-oxo-1,2-dihydropyrimidines (DHPMs) by potassium peroxydisulfate (PPS) in aqueous acetonitrile solution under thermal conditions. Based on the proposed oxidation reaction mechanism by way of a radical, a capto-dative stabilized radical intermediate, among two possible formed double benzylic/allylic radical centres, governs the type of product formed. Whereas the electron-donating nature of the additional methoxy-substituent enhances the rate of oxidation, its attachment to the radical intermediate decreases the radical stability, simultaneously causing the shift of the radical centre to the capto-dative stabilized benzylic radical centre. The data of the density functional theory computational studies concerning the bond lengths to the radical centres and Mulliken population analysis support the results of the experimental work. © CSIRO 2016.
Masoudi, M. ,
Behzad, M. ,
Arab, A. ,
Tarahhomi, A. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2016
Journal of Molecular Structure (00222860) 1122pp. 123-133
Three new Cobalt(III) Schiff base complexes were synthesized and characterized by spectroscopic methods and x-ray crystallography. The DFT optimized structures of the complexes agreed well with the corresponding x-ray structures. According to the calculated vibrational normal modes, the observed signals in the IR spectra of the complexes were assigned. The experimental UV-Vis spectra of the complexes were also discussed considering the calculated excited states and molecular orbitals. Hirshfeld surface analysis was carried out to study the inter-contact interactions in these complexes. These studies provided comprehensive description of such inter-contact interactions by means of an appealing graphical approach using 3D Hirshfeld surfaces and 2D fingerprint plots derived from the surfaces. It indicated the dominant role of various hydrogen intermolecular interactions such as H⋯H (above 60%), C⋯H/H⋯C (near 15%-20%), O⋯H/H⋯O (about 16% or 17% for structures with counter ion ClO4-) and H⋯F (17% for structure with counter ion PF6-) contacts into the crystal packing which are discussed in details. © 2016 Elsevier B.V. All rights reserved.
Publication Date: 2016
RSC Advances (20462069) 6(9)pp. 7189-7194
Two tetranuclear cubane-like nickel(ii) complexes of formula [Ni4(CH3O)4(L1)4(CH3OH)4] (1) and [Ni4(CH3O)4(L2)4(CH3OH)4] (2) (HL1 = 2-hydroxybenzaldehyde and HL2 = 2-hydroxy-5-methylbenzaldehyde) have been prepared by the reaction of NiCl2·6H2O with methanolic solutions of HL1 and HL2 in the presence of triethylamine at room temperature. Complexes 1 and 2 have been characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The X-ray crystal structure analysis revealed that 1 and 2 have a cubane-type structural topology with four Ni(ii) ions and four methoxo-oxygen atoms regularly alternating at the corners. Each metal ion in 1 and 2 is six-coordinate in a distorted octahedral geometry defined by three bridging methoxo-oxygens, one oxygen atom from a methanol molecule and two oxygen atoms from the bidentate L1 (1)/L2 (2) ligands. The magnetic properties of 1 and 2 were investigated in the temperature range 1.9-300 K. They are indicative of an overall ferromagnetic behaviour, the decrease in the very low temperature region being due to zero-field splitting and intermolecular interactions. A detailed analysis of the magnetic data of 1 and 2 assuming an idealized D2d symmetry for the Ni4O4 unit shows the occurrence of a low-lying spin nonet and two opposite magnetic interactions, one being ferromagnetic [Ja = +12.6 (1) and +10.5 cm-1 (2)] and the other antiferromagnetic [Jb = -4.10 (1) and -2.10 cm-1 (2)]. These values fit well the linear correlation between the exchange coupling parameter (J) and the Ni-O-Ni angle (α) which was established for Ni4O4 cubane motifs in previous works. © The Royal Society of Chemistry 2016.
Publication Date: 2016
Materials Chemistry and Physics (02540584) 184pp. 222-232
A new mononuclear yttrium(III) complex, [Y(MO)3(DMF)3(H2O)2] (where MO– is methyl orange anion (4-[(4-dimethylamino)phenyldiazenyl]benzenesulfonate)), was synthesized in an aqueous solution. The complex was characterized by elemental analysis, UV/Vis, FT-IR, and single-crystal X-ray crystallography. The yttrium oxysulfate nanoparticles (Y2O2SO4) were then prepared by calcination of [Y(MO)3(DMF)3(H2O)2]. The obtained nanoparticles were characterized by FT-IR, X-ray diffraction analysis (XRD), and field-emission scanning electron microscopy (FE-SEM). The hydrogen adsorption/desorption (Hads/Hdes) behavior of the Y(III) complex and Y2O2SO4 nanoparticles was studied at a carbon paste electrode (CPE) in H2SO4 by cyclic voltammetry (CV). The recorded voltammograms exhibited a pair of peaks corresponding to the adsorption/desorption of hydrogen for the Y(III) complex and Y2O2SO4 nanoparticles. The results show a reversible hydrogen adsorption/desorption reaction for both compounds. The voltammograms of the nanoparticles indicate an excellent cycling stability for the adsorption/desorption of hydrogen. In addition, the linear sweep voltammetry (LSV) technique was used to investigate the electrocatalytic activity of both compounds for the hydrogen adsorption reaction. The linear voltammograms of both compounds demonstrate the excellent electrocatalytic activity for the hydrogen adsorption reaction. © 2016 Elsevier B.V.
Publication Date: 2016
Journal of the Electrochemical Society (00134651) 163(10)
For the first time, this paper presents the results of electrochemical oxidation of p-aminoacetanilide in aqueous solution with different pH values. The data indicate that electrochemically generated p-quinone-diimine is unstable in acidic and alkaline solution. It is hydrolyzed in acidic (pH range of 1-6) and alkaline (pH range of 12-13) media and it is dimerized and trimerized in intermediate pH values. The observed homogeneous rate constants (kobs) of the coupling reaction of p-aminoacetanilide with electrochemically generated p-quinone-diimine, was estimated by comparison of the experimental cyclic voltammograms with the digital simulated results in the pH range 7-9. In addition, based on electrochemical data, a green electrochemical protocol for the synthesis of a new yellow azo dye involving electrochemical oxidation of p-aminoacetanilide in aqueous phosphate buffer and in an undivided cell, using carbon anode is described. © 2016 The Electrochemical Society.
Babahydari, A.K. ,
Fareghi-alamdari, R. ,
Hafshejani, S.M. ,
Amiri rudbari, H. ,
Farsani, M.R. Publication Date: 2016
Journal Of The Iranian Chemical Society (1735207X) 13(8)pp. 1463-1470
HSiW-MOF, PMo-MOF, HPMo-MOF and PW-MOF were synthesized and characterized by elemental analysis, UV–Vis, FT-IR, cyclic voltammetry and XRD. These compounds were used as catalyst for the selective oxidation of alcohols by hydrogen peroxide. Within them, PW-MOF showed a higher catalytic activity compared to other catalysts in a similar reaction condition. Therefore, PW-MOF catalyst system was successfully used for the selective oxidation of the benzylic, linear and secondary alcohols to the corresponding aldehydes and ketones. Also, allylic alcohols were converted to the corresponding aldehydes with high conversion and significant selectivity. Moreover, PW-MOF was stable to leaching, behaved as true heterogeneous catalysts, easily recovered by filtration, and reused four times with the preserve of the catalytic performance. © 2016, Iranian Chemical Society.
Publication Date: 2016
Journal Of The Iranian Chemical Society (1735207X) 13(8)pp. 1395-1404
X-ray crystal structure analysis and quantum chemical calculations based on the density functional theory (DFT) were used for structural and electronic characterizations of three 2,3-dihydroquinazolin-4(1H)-ones (DHQZs). The occurrence of the C2-stereocenter in the heterocyclic ring causes the formations of both R- and S-enantiomers. X-ray diffraction technique indicates that these compounds exist as a racemic mixture in the crystal structure, and the enantiomers are orientated to each other via hydrogen bonding between the potential hydrogen donor (N3–H) and acceptor species (C4 = O group) in each layer under the formation of an enantio-syndio packing. Additional intermolecular and intramolecular interactions affect the orientations of the molecules adopted in the crystal packing, especially the orientation of the ring substitution. Most computational data, including the bond lengths and angles, are well in agreement with the experimental data. Dihedral angle scanning elucidates the effect of the nature and the location of the additional substituent on the aryl group at C2-position on the total energy content of the molecule. © 2016, Iranian Chemical Society.
Publication Date: 2016
RSC Advances (20462069) 6(41)pp. 34940-34945
A new fluorescent and colorimetric chemosensor based on naphthothiazole S1 was synthesized and its applications as chemosensor for the selective sensing of pollutant metal ions in water resources and/or biological systems were investigated. Sensor S1 showed great selectivity for Zn2+ and Sn2+ over other metal ions. The Job's plot showed a 1 : 1 stoichiometry between S1 with Zn2+ and Sn2+. Interaction mode of sensor S1 with Zn2+ ion was further approved by single crystals X-ray crystallography method. The detection limit for the fluorescent chemosensor S1 toward Zn2+ and Sn2+ were respectively 2.60 × 10-8 M and 8.21 × 10-8 M. © The Royal Society of Chemistry 2016.
Khoshnavazi, R. ,
Nicolò, F. ,
Amiri rudbari, H. ,
Bahrami, L. ,
Noruzi, A. ,
Abdi, K. Publication Date: 2016
Journal Of The Iranian Chemical Society (1735207X) 13(1)pp. 131-138
New 2D undulating layer pure inorganic polymers H2[{M(H2O)8 M(H2O)7M(H2O)6}P2W18Ce3O70(OH)(H2O)2] xH2O; M = Ce3+ (1), Nd3+ (2) and Sm3+ (3) were synthesized by routine synthetic reactions in aqueous solution and characterized by elemental analysis, IR spectra, cyclic voltammetry, XRPD, magnetic susceptibility, TG analysis, and X-ray single-crystal diffraction. The 2D framework of 1-3 were built by tri-Ce4+ substituted sandwich-type polyoxoanions modified by six trivalent lanthanide cations M(H2O)x (x = 6-8) units. The M(H2O)x (x = 6-7) groups act as bridges to form 2D undulating layer, but the M(H2O)8 groups link the 2D layers together via hydrogen bonds to form a 3D supra-molecular framework. © 2015 Iranian Chemical Society.
Publication Date: 2016
RSC Advances (20462069) 6(85)pp. 81943-81949
A novel straightforward method for the synthesis of 2,3-disubstituted imidazo[1,2-a]pyridine derivatives in water as a truly safe and cheap reaction medium was developed. Hence, N-alkyl pyridinium and S-alkyl thiouronium salts were reacted in the presence of NaHCO3 as a mild base in water to produce imidazo[1,2-a]pyridines in moderate to excellent yields. © 2016 The Royal Society of Chemistry.
Publication Date: 2016
Inorganica Chimica Acta (18733255) 447pp. 52-58
A new palladium(II) complex of PdLCl (HL: S-allyl-3-(2-pyridyl-methylene)dithiocarbazate) has been synthesized and characterized by elemental analysis, IR, EI-MS, UV-Vis, 1H NMR, 13C NMR, TGA and SCXRD analysis. IR spectra reveled that the ligand was coordinated to the palladium ion in a tridentate thiolic form manner with NNS donor sites. The molar conductance data revealed that the complex was non-electrolytes. The complex shows square planar geometries around palladium. The dithiocarbazate coordinates as a uninegatively tridentate NNS ligand chelating via the pyridine and azomethine nitrogen atoms and the thiolate sulfur atoms. DFT and TD-DFT calculations on the complex were also carried out by the B3LYP/6-311++G(d,p) level of theory. The results were used to molecular orbital diagram, HOMO-LUMO, NBO, spin-allowed singlet-singlet electronic transitions studies (TD-DFT). © 2016 Elsevier B.V. All rights reserved.
Publication Date: 2016
Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (15205738) 53(4)pp. 227-236
Single crystal of a new one-dimensional copper organic coordination polymer, 1D-CuOCP, [Cu(HL)NO3]n (1) (H2L = [2-[1-(2-hydroxy-propylimino)-ethyl]-phenol]) and its nanostructure, have been synthesized by slow evaporation of methanol solution of compound (1) and sonochemical process respectively. Nanostructure of the complex was characterized by X-ray powder diffraction (XRD), FT-IR spectroscopy and scanning electron microscopy (SEM) and the structure of compound 1 was determined by single-crystal X-ray diffraction. Thermal stability of compound 1 in its nanosize form has also been studied by thermal gravimetric analysis (TGA). The effect of concentration of initial reagents on size and morphology of nanostructured compound 1 has been examined. The brightness of this study is to use the nanostructure of 1D-CuOCP as precursor to prepare single phase CuO nanoparticles via a solid-state decomposition procedure. Characterization methods confirmed that CuO nanoparticles with an average diameter of 40 nm were obtained from direct calcination of the precursor at 500°C under air. © 2016 Taylor and Francis Group, LLC.
Publication Date: 2016
Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences (09320776) 71(9)pp. 959-965
Three new compounds of zinc(II) and cadmium(II) with the ligand 4,4′-dimethoxy-2,2′-bipyridine (4,4′-dmo-2,2′-bpy), including cis-[Zn(4,4′-dmo-2,2′-bpy)2(SCN)2] (1), cis-[Cd(4,4′-dmo-2,2′-bpy)2(SCN)2] (2), and [Cd3(4,4′-dmo-2,2′-bpy)3(N3)5(OAc)]n (3), have been obtained as white single crystals by the branched tube method and characterized by elemental analysis, FT-IR and 1H, 13C NMR spectroscopy, and X-ray crystallography. Single-crystal structure analyses of the isostructural complexes 1 and 2 showed distorted octahedral geometry for zinc(II) and cadmium(II) with ZnN6 and CdN6 environments. Complex 3 reveals a rare coordination polymer containing octahedrally coordinated cadmium(II) expanding to chains by two different bridging modes, including Cd-O-C-O-Cd and Cd-N-Cd. © 2016, Verlag der Zeitschrift fur Naturforschung. All rights reserved.
Menati, S. ,
Amiri rudbari, H. ,
Askari, B. ,
Farsani, M.R. ,
Jalilian, F. ,
Dini, G. Publication Date: 2016
Comptes Rendus Chimie (18781543) 19(3)pp. 347-356
The condensation reaction of 1,2-bis(2'-aminophenoxy)benzene with 2-pyridinecarbaldehyde in a mole ratio of 1:2 gives a new Schiff base ligand (L). Four Schiff base complexes, CoL(NO3)2 (1), NiLCl2 (2), ZnL(NO3)2 (3) and Pd2LCl4 (4) have been prepared by direct reaction of the ligand (L) and appropriate metal salts. The Schiff base ligand (L) has been characterized by IR, 1H NMR and 13C NMR spectroscopy and elemental analysis. Also, all complexes have been characterized by IR and XRD spectroscopy techniques and elemental analysis. The synthesized complexes have very poor solubility in all polar and non-polar solvents such as: H2O, MeOH, EtOH, CH3CN, DMSO, DMF, CHCl3, CH2Cl2, THF, etc; therefore, they have been used as heterogeneous catalysts. Catalytic performance of the complexes was studied in oxidation of thioanisole using hydrogen peroxide (H2O2) as the oxidant. Various factors including the reaction temperature, amount of oxidant and catalyst amount were optimized. The palladium Schiff base complex, Pd2LCl4 (4), shows better catalytic activity than other complexes. Therefore, the Pd(II) Schiff base complex has been used as a catalyst for oxidation of different sulfides to their corresponding sulfones in acetonitrile with hydrogen peroxide as the oxidant. The palladium Schiff base complex, Pd2LCl4 (4), has shown a very good recyclability, up to five times, without any appreciable decreases in catalytic activity and selectivity. © 2015 Académie des sciences.
Publication Date: 2016
Inorganica Chimica Acta (18733255) 440pp. 139-147
Two new symmetrical Mn(II) and Cd(II) pentaaza macrocyclic Schiff base complexes were prepared via templated [1 + 1] cyclocondensation of 2,6 diacetylpyridine and an amine containing homopiperazine moiety in the presence of related metal ions. These complexes have been characterized by elemental analysis, IR spectra, EI-MS, conductivity measurements and in the case of Cd(II) complex by 1H and 13C NMR spectroscopy. In addition, Crystal structures of complexes have been determined by X-ray crystallographic technique. This reveals that in the solid state both complexes adopt a distorted pentagonal pyramidal geometry, with the pentaaza macrocycle positioned in the equatorial plane and the chloride ion in the axial site. Also, the bonding situation between the [MCl]+ (M = Mn2+, Cd2+) fragment and Ligand (L) in [MLCl]+ (M = Mn, Cd) complexes, were carried out by NBO and energy-decomposition analysis (EDA), as well as its natural orbitals for chemical valence variation (EDA-NOCV). The results confirmed that the contribution of the electrostatic interactions in the M ← L bonds of the complexes is predominantly more than 50%. © 2015 Elsevier B.V.
Kazemi, Z. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Mirkhani, V. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. ,
Gharaghani, S. Publication Date: 2016
Journal of Photochemistry and Photobiology B: Biology (18732682) 162pp. 448-462
Novel metal-based drug candidate including VOL2, NiL2, CuL2 and PdL2 have been synthesized from 2-hydroxy-1-allyliminomethyl-naphthalen ligand and have been characterized by means of elemental analysis (CHN), FT-IR and UV–vis spectroscopies. In addition, 1H and 13C NMR techniques were employed for characterization of the PdL2 complex. Single-crystal X-ray diffraction technique was utilized to characterise the structure of the complexes. The Cu(II), Ni(II) and Pd(II) complexes show a square planar trans-coordination geometry, while in the VOL2, the vanadium center has a distorted tetragonal pyramidal N2O3 coordination sphere. The HSA-binding was also determined, using fluorescence quenching, UV–vis spectroscopy, and circular dichroism (CD) titration method. The obtained results revealed that the HSA affinity for binding the synthesized compounds follows as PdL2 > CuL2 > VOL2 > NiL2, indicating the effect of metal ion on binding constant. The distance between these compounds and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Furthermore, computational methods including molecular docking and our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM) were carried out to investigate the HSA-binding of the compounds. Molecular docking calculation indicated the existence of hydrogen bond between amino acid residues of HSA and all synthesized compounds. The formation of the hydrogen bond in the HSA-compound systems leads to their stabilization. The ONIOM method was utilized in order to investigate HSA binding of compounds more precisely in which molecular mechanics method (UFF) and semi empirical method (PM6) were selected for the low layer and the high layer, respectively. The results show that the structural parameters of the compounds changed along with binding to HSA, indicating the strong interaction between the compounds and HSA. The value of binding constant depends on the extent of the resultant changes. This should be mentioned that both theoretical methods calculated the Kb values in the same sequence and are in a good agreement with the experimental data. © 2016 Elsevier B.V.
Kazemi, Z. ,
Amiri rudbari, H. ,
Sahihi, M. ,
Mirkhani, V. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. ,
Azimi gandomani, G. ,
Gharaghani, S. ,
Abbasi kajani, A. Publication Date: 2016
Journal of Photochemistry and Photobiology B: Biology (18732682) 163pp. 246-260
A racemic mixture of a new chiral Schiff base ligand (HL: R/S-(1-phenylethylimino)methylnaphtalen-2-ol) has been utilized to prepare Pd(II) complex. Crystallization technique has been employed to separate diastereomeric pairs of Pd(II) complex: (meso PdL2) and (rac PdL2) that in this paper are known as PdL2 1 and PdL2 2, respectively. The synthesized complexes have been characterized by means of elemental analysis (CHN), FT-IR, 1H and 13C NMR spectroscopies. Moreover, PdL2 1 has been structurally characterized by single-crystal X-ray diffraction. The geometry around the metal center is square-planar. The interaction of two diastereomers of Pd(II) complex with FS-DNA has been explored, using UV–vis spectroscopy, fluorescence quenching, chemometrics and viscosity measurement methods. The PdL2 1 exhibited higher binding constant, about 10-fold, (1.0 × 106 M− 1) as compared to PdL2 2 (1.5 1.5 × 105 M− 1). Moreover, the human serum albumin (HSA) binding ability has been monitored by absorption, quenching of tryptophan fluorescence emission and circular dichroism (CD) studies. The slight difference is observed between HSA binding affinity with the complexes: PdL2 1 (6.2 × 104 M− 1) and PdL2 2 (3.3 × 104 M− 1). Also, the thermodynamic parameters were determined at three different temperatures (298, 308 and 318 K). In this study, molecular docking was also carried out to confirm and illustrate the specific DNA- and HSA-binding of the Pd(II) complexes. In the PdL2 1-HSA system a T-shaped π-π interaction with PHE206 was observed. While in the PdL2 2-HSA system there are a hydrogen bond, a π-cation and two T-shaped π-π interactions with ASB324, LYS212 and PHE228, respectively. The groove binding mode of DNA interaction has been proposed for both diastereomers. © 2016 Elsevier B.V.
Publication Date: 2016
Journal of Molecular Structure (00222860) 1119pp. 373-384
Two new o-hydroxy Schiff-bases compounds, L1 and L2, were derived from the 1:1 M condensation of 2,3-dihydroxybenzaldehyde and 2,4-dihydroxybenzaldehyde with tert-butylamine and were characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopies. The crystal structure of L2 was also determined by single crystal X-ray analysis. The crystal structure of L2 showed that the compound exists as a zwitterionic form in the solid state, with the H atom of the phenol group being transferred to the imine N atom. It adopts an E configuration about the central C=N double bond. Furthermore, binding of these Schiff base ligands to Human Serum Albumin (HSA) was investigated by fluorescence quenching, absorption spectroscopy, molecular docking and molecular dynamics (MD) simulation methods. The fluorescence emission of HSA was quenched by ligands. Also, suitable models were used to analyze the UV-vis absorption spectroscopy data for titration of HSA solution by various amounts of Schiff bases. The spectroscopic studies revealed that these Schiff bases formed 1:1 complex with HSA. Energy transfer mechanism of quenching was discussed and the values of 3.35 and 1.57 nm as the mean distances between the bound ligands and the HSA were calculated for L1 and L2, respectively. Molecular docking results indicated that the main active binding site for these Schiff bases ligands is in subdomain IB. Moreover, MD simulation results suggested that this Schiff base complex can interact with HSA, with a slight modification of its tertiary structure. © 2016 Elsevier B.V. All rights reserved.
Grivani, G. ,
Vakili, M. ,
Khalaji, A.D. ,
Bruno, G. ,
Amiri rudbari, H. ,
Taghavi, M. Publication Date: 2016
Journal of Molecular Structure (00222860) 1116pp. 333-339
The copper (II) Schiff base complex of [CuL2] (1), HL = 2-{(E)-[2-chloroethyl) imino]methyl}phenol, has been synthesized and characterized by elemental (CHN) analysis, UV-Vis and FT-IR spectroscopy. The molecular structure of 1 was determined by single crystal X-ray diffraction technique. The conformational analysis and molecular structures of CuL2 were investigated by means of density functional theory (DFT) calculations at B3LYP/6-311G∗level. An excellent agreement was observed between theoretical and experimental results. The Schiff base ligand of HL acts as a chelating ligand and coordinates via one nitrogen atom and one oxygen atom to the metal center. The copper (II) center is coordinated by two nitrogen atoms and two oxygen atoms from two Schiff base ligands in an approximately square planar trans-[MN2O2] coordination geometry. Thermogravimetric analysis of CuL2 showed that it was decomposed in five stages. In addition, the CuL2 complex thermally decomposed in air at 660 °C and the XRD pattern of the obtained solid showed the formation of CuO nanoparticles with an average size of 34 nm. © 2016 Elsevier B.V. All rights reserved.
Amiri rudbari, H. ,
Iravani, M.R. ,
Moazam, V. ,
Askari, B. ,
Khorshidifard, M. ,
Habibi, N. ,
Bruno, G. Publication Date: 2016
Journal of Molecular Structure (00222860) 1125pp. 113-120
A new Schiff base ligand, HL2, and four new Schiff base complexes, NiL12, PdL12, NiL22 and ZnL22, have been prepared and characterized by elemental analysis (CHN), FT-IR and UV–Vis spectroscopy. 1H and 13C NMR techniques were employed for characterization of the ligand (HL2) and the diamagnetic complexes (PdL12 and ZnL22). The molecular structures of PdL12, NiL22 and ZnL22 complexes were determined by the single crystal X-ray diffraction technique. The crystallographic data reveal that in these complexes the metal centers are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two Schiff base ligands. The geometry around the metal center in the PdL12 and NiL22 complexes is square-planar and for ZnL22 it is a distorted tetrahedral.In the end, five new (HL2, NiL12, PdL12, NiL22 and ZnL22) and six reported (HL1, VOL12, CoL13, CuL12, ZnL12 and Zn2L14) Schiff base compounds were tested for their in vitro antimicrobial activity against Staphylococcus aureus and Escherichia coli as examples of Gram-positive and Gram-negative bacterial strains, respectively, by disc diffusion method. © 2016 Elsevier B.V.
Mahlooji, N. ,
Behzad, M. ,
Tarahhomi, A. ,
Maroney, M. ,
Amiri rudbari, H. ,
Bruno, G. ,
Ghanbari, B. Publication Date: 2016
Journal of Molecular Structure (00222860) 1110pp. 119-127
Two new heteronuclear Nickel(II)/Sodium(I) complexes of a side-off compartmental Schiff base ligand were synthesized and characterized by spectroscopic methods. Crystal structures of both of the complexes were also obtained. The Schiff base ligand was synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with 2-hydroxy-3-methoxybenzaldehyde. In both of the complexes the Ni(II) ion is coordinated to the inner N2O2 coordination sphere with square-planar geometry and the Na(I) ion is coordinated to the outer O2O2′ coordination sphere. In Complex (1) with general formula [Ni(L)Na(CH3OH)(ClO4)] the sodium ion is seven coordinated while in (2) with general formula [{Ni(L)Na(OH2)}2(μ-Ni(CN)4)] the sodium ion is six coordinated. Intermolecular interactions in two studied complexes were analyzed using 3D Hirshfeld surfaces and corresponding 2D fingerprint plots. This analysis showed that the H ... H and C ... H/H ... C contacts for both structures (altogether 67.5% of total Hirshfeld surface area for (1) and 77.6% for (2)) and the O ... H/H ... O (24.2%) for (1) and the N ... H/H ... N (8.1%) contacts for (2) were the characteristic intermolecular contacts in the related crystal structures. © 2016 Elsevier Ltd. All rights reserved.
Beheshti, A. ,
Safaeiyan, F. ,
Hashemi, F. ,
Motamedi, H. ,
Mayer, P. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2016
Journal of Molecular Structure (00222860) 1123pp. 225-237
Two new mono- and dinuclear Co(II) complexes namely [Co(tdmpp)Cl2]2·H2O (1) and [Co2(tdmpp)Cl4] (2) (where tdmpp = 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane) were prepared by one-pot reactions in methanol as a solvent. These compounds have been characterized by single crystal X-ray diffraction, elemental analysis, infrared spectroscopy, antibacterial activity and computational studies. In both complexes, Co (II) atom is tetrahedrally coordinated by two N atoms from one of the chelating bidentate bis(3,5-dimethylpyrazolyl)methane units of the tdmpp ligand and two Cl as terminal ligands. In these structures, the neighboring [Co(tdmpp)Cl2]2·H2O (1) and [Co2(tdmpp)Cl4] (2) molecules are joined together by the intermolecular C-H⋯Cl hydrogen bonds to form a 1D chain structure. As a consequence of the intermolecular C-H⋯π interactions these chains are further linked to generate a two-dimensional non-covalent bonded structure. The in vitro antibacterial activity studies of the free tdmpp ligand, compounds 1 and 2 show that the ability of these compounds to inhibit growth of the tested bacteria increase progressively from tdmpp to the dinuclear complex 2. Molecular-docking investigations between the five standard antibiotic, free tdmpp ligand, title complexes and five biological macromolecule enzymes (receptors) were carried out from using Autodock vina function. The results of docking studies confirmed that the metal complexes are more active than the free ligand. This is consistent with the results obtained by the antibacterial activities of these compounds. © 2016 Elsevier B.V.
Publication Date: 2016
Inorganica Chimica Acta (18733255) 445pp. 124-128
Two unique heteronuclear Schiff base complexes of Cu(II), [{Cu(L)Na(ClO4)}2(μ-H2L)] (1) and Ni(II), [{Ni(L)Na(BF4)}2(μ-H2L)] (2) were synthesized and characterized by different spectroscopic methods as well as X-ray crystallography. The Schiff base ligand (H2L) was synthesized from the condensation meso-1,2-diphenyl-1,2-ethylenediamine with 3-methoxysalicylaldehyde. The 3d metal ions in these complexes have been accommodated by the inner N2O2 compartment of the Schiff base ligand, while the O2O′2 outer compartment has accommodated the Na(I) ion (O and O′ denote the phenolic and methoxy oxygen atoms, respectively). Besides, a Schiff base ligand has doubly bridged the M(II)/Na(I) moieties via the (OO′)2 coordination mode. This mode of bidentate action of a potentially tetradentate Schiff base ligand is very rare and has been observed for the first time in such 3d-ns complexes. The in vitro antibacterial activity of the Schiff base ligand and the complexes (1) and (2) were tested against human pathogenic bacteria such as Bacillus subtilis (Gram positive); Staphylococcus aureus (Gram positive); Salmonella typhi (Gram negative); and Escherichia coli (Gram negative). The results showed that these new hetero-polynuclear complexes had moderate antibacterial activity against both Gram type bacteria. © 2016 Published by Elsevier B.V.
Publication Date: 2016
RSC Advances (20462069) 6(17)pp. 13609-13613
Wheel-shaped polyoxotungstate [Cu20Cl(OH)24(H2O)12(P8W48O184)]25- (Cu20 POM) was used as an efficient catalyst for the preparation of triazoles from the corresponding alkyl halides, sodium azide, and alkynes. In this click reaction, the three-component synthesis of 1,2,3-triazoles was performed under mild reaction conditions at room temperature and high to excellent yields were obtained. The isolation and purification processing of organic azides were avoided in this procedure, as they were prepared in situ. © The Royal Society of Chemistry 2016.
Ghadermazi, M. ,
Derikvand, Z. ,
Mahmouidiazar, Z. ,
Shahnejat, E. ,
Amiri rudbari, H. ,
Bruno, G. ,
Shokrollahi, A. ,
Nasiri, S. ,
Mehdizadeh naderi, P. Publication Date: 2015
Journal of Coordination Chemistry (10290389) 68(22)pp. 3982-4002
Four new supramolecular compounds, (2-mimH)[Ca(pydcH)3][Ca(pydcH2)(pydc)(H2O)2]·4H2O (1), (1-mimH)2[Zr(pydc)3] (2), (2-mimH)2[Cd(pydc)2]·8H2O (3), and (2-mimH)2[Hg(pydc)2]·8H2O (4) [where pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), 1-mim = 1-methylimidazole, and 2-mim = 2-methylimidazole], have been synthesized and characterized by elemental analyses, spectroscopic techniques (IR, UV-vis, 1H NMR, and 13C NMR), thermal (TG/DTG/DTA) analysis as well as single-crystal X-ray diffraction. All four compounds are proton-transfer salts of the methylimidazolium cations and metal complex anions that crystallized from a solution of pyridine-2,6-dicarboxylic acid, methylimidazole, metal nitrates or chlorides as starting materials. The coordinating dicarboxylic acid is deprotonated at the carboxyl group and methylimidazole is protonated to balance the charge. In the crystal structures of 1-4, hydrogen bonding and π-π stacking play important roles. Water clusters are formed in 1, 3, and 4. The equilibrium constants of dipicolinic acid (pydc) and methylimidazole derivatives (1-mim and 2-mim), pydc-2-mim, pydc-1-mim proton-transfer systems as well as those of their complexes were investigated by a potentiometric pH titration method. The stoichiometries of most of the complex species in solution were very similar to the cited crystalline metal ion complexes. © 2015 Taylor and Francis.
Yousef ebrahimipour s., S.Y. ,
Ranjabr, Z.R. ,
Kermani, E.T. ,
Amiri, B.P. ,
Amiri rudbari, H. ,
Saccá, A. ,
Hoseinzade, F. Publication Date: 2015
Transition Metal Chemistry (1572901X) 40(1)pp. 39-45
A new mixed-ligand Ni(II) complex, [Ni(L)(mimi)], was prepared by the reaction of Ni(OAc)2·4H2O, 4-bromo-2-[(2-hydroxy-5-methylphenyl]iminomethyl] phenol [H2L] and 1-methylimidazole (mimi) in two forms of bulk and nanoparticle sizes using slow evaporation and ultrasonic irradiation, respectively. The complex was characterized by physicochemical and spectroscopic methods, and also by single crystal X-ray diffraction. The Ni(II) center is coordinated by the ONO donor ligand and the nitrogen of 1-methylimidazole. Scanning electron microscopy revealed that the particle size of the complex synthesized using ultrasonic irradiation was below 100 nm. Both the nano and bulk forms of [Ni(L)(mimi)] were found to be effective catalysts for four-component synthesis of dihydropyrano[2,3-c]pyrazoles from a stoichiometric mixture of ethyl acetoacetate, hydrazine hydrate, aldehyde and malononitrile in ethanol, and furthermore, the catalytic activity of the nano form of the complex is higher. © Springer International Publishing 2014.
Anjomshoa, M. ,
Hadadzadeh h., H. ,
Torkzadeh-mahani, M. ,
Fatemi, S.J. ,
Adeli-sardou, M. ,
Amiri rudbari, H. ,
Nardo, V.M. Publication Date: 2015
European Journal of Medicinal Chemistry (02235234) 96pp. 66-82
The copper(II) complex of 1,2,4-triazine derivatives, [Cu(dppt)2(H2O)](PF6)2(dppt is 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine), has been synthesized and fully characterized by spectroscopic methods and single crystal X-ray diffraction. The in vitro DNA-binding studies of the complex have been investigated by several methods. The results showed that the complex intercalates into the base pairs of DNA. The complex also indicated good binding propensity to BSA. The results of molecular docking and molecular dynamic simulation methods confirm the experimental results. Finally, the in vitro cytotoxicity indicate that the complex has excellent anticancer activity against the three human carcinoma cell lines, MCF-7, A-549, and HT-29, with IC50 values of 9.8, 7.80, and 4.50 μM, respectively. The microscopic analyses of the cancer cells demonstrate that the Cu(II) complex apparently induced apoptosis. © 2015 Elsevier Masson SAS.
Publication Date: 2015
Polyhedron (02775387) 99pp. 186-197
Abstract A new lanthanum(III) complex, [La(MO)3(DMF)3(H2O)2] (MO- = methyl orange), was synthesized by the reaction of methyl orange and lanthanum(III) nitrate hexahydrate in the aqueous solution. The complex was characterized by elemental analysis, FT-IR, UV-Vis, and single-crystal X-ray diffraction. Then the lanthanum oxysulfate nanoparticles (La2O2SO4) were prepared by calcination of [La(MO)3(DMF)3(H2O)2] as a new precursor. The nanoparticles were characterized by FT-IR, X-ray diffraction analysis (XRD), and field emission scanning electron microscopy (FE-SEM). Finally, the hydrogen adsorption/desorption properties of the La(III) complex and La2O2SO4 nanoparticles were investigated at a glassy carbon electrode (GCE) in H2SO4 by cyclic voltammetry (CV). The voltammograms showed a pair of peaks corresponding to the adsorption/desorption of hydrogen for both compounds. Also, the electrocatalytic activity of both compounds for the hydrogen adsorption and hydrogen evolution reaction (HER) was investigated by linear sweep voltammetry (LSV). © 2015 Elsevier Ltd.
Ghadermazi, M. ,
Derikvand, Z. ,
Zahedi, A. ,
Shokrollahi, A. ,
Nasiri, S. ,
Amiri rudbari, H. Publication Date: 2015
Monatshefte fur Chemie (00269247) 146(8)pp. 1257-1266
A new heterometallic supramolecular coordination polymer, namely [(1-mimH)[Nd(pydc)3Ca(pydcH2)(H2O)2]·4H2O] n (where pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), 1-mim = 1-methylimidazole) has been prepared and characterized by elemental analysis, spectral (IR, UV-Vis), 1H NMR and 13C NMR spectroscopy, thermal analysis as well as single-crystal X-ray diffraction. The X-ray diffraction study demonstrates that the compound has a 1D network; the layers of this compound are connected by complicated hydrogen bonds to form 3D supramolecular architecture. The polymeric chain contains Nd(III) ions and Ca(II) ions bridged by (pydc)2- ligands. Each (pydc)2- ion is connected to one neodymium(III) ion as a tridentate ligand and one calcium ion via bridging carboxylate group. The equilibrium constants of dipicolinic acid and 1-methylimidazole, pydc/1-mim proton transfer system, as well as those of the complexes (binary, ternary, and quaternary) were investigated by potentiometric pH titration method. Graphical abstract: [Figure not available: see fulltext.]. © 2014 Springer-Verlag Wien.
Publication Date: 2015
Journal Of Chemical Sciences (09743626) 127(7)pp. 1321-1328
An environmentally friendly protocol is described for an economic, practical laboratory-scale oxidation of primary and secondary alcohols to aldehydes and ketones, using a bis-chloro-bridged binuclear Cu(II) complex [(HL)Cu(μ 2-Cl)2Cu(HL)] 1.5 CH3OH as catalyst. The catalyst was prepared in situ from commercially available reagents and is characterized by single crystal X-ray analysis, FT-IR, UV-visible spectra, mass spectrometry, and powder x-ray diffraction (PXRD). The geometry of the complex has been optimized using the B3LYP level of theory confirming the experimental data. Our results demonstrated well the efficiency, selectivity and stability of this new catalyst in the oxidation of alcohols in ethanol and tert-butyl hydroperoxide (tBuOOH) as a green solvent and oxidant, respectively. Turnover number and reusability have proven the high efficiency and relative stability of the catalyst. [Figure not available: see fulltext.] © 2015 Indian Academy of Sciences.
Mirzaei, M. ,
Eshghi, H. ,
Rahimizadeh, M. ,
Bakavoli, M. ,
Matin, M.M. ,
Hosseinymehr, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2015
Journal of the Chinese Chemical Society (00094536) 62(12)pp. 1087-1096
A series of α-aminophosphonates were synthesized through one-pot condensation of aryl aldehydes, aryl amines and diethyl phosphite in the absence of any catalyst and organic solvents. All the synthesized α-aminophosphonates were characterized by spectral and elemental analysis and in the case of compound 4j by X-ray crystallography. Some of these new α-aminophosphonate derivatives were found to have cytotoxic activity on the cancer cell line DU145 in vitro by the MTT method. © 2015 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany.
Jalilian, F. ,
Yadollahi, B. ,
Farsani, M.R. ,
Tangestaninejad, S. ,
Amiri rudbari, H. ,
Habibi, R. Publication Date: 2015
RSC Advances (20462069) 5(86)pp. 70424-70428
In this work, the catalytic perspective of three Keplerate polyoxometalates, Mo72M30 (M = V, Cr, Fe) in the epoxidation of various alkenes is considered. The catalytic reactions were performed in water under mild conditions and high to excellent conversions and selectivities were obtained using H2O2 as oxidant and Mo72Cr30 as the best catalyst. Keplerate POM catalysts have shown a very good recyclability, up to five times, without any appreciable decreases in catalytic activity and selectivity. © The Royal Society of Chemistry 2015.
Publication Date: 2015
Comptes Rendus Chimie (18781543) 18(4)pp. 391-398
Abstract 1,2-bis(2'-aminophenoxy)-4-methylbenzene provides a Schiff base by reaction with 2-pyridinecarboxaldehyde. The stereochemical rigidity of ortho-aminophenyl diamines causes this latter, as well as the corresponding nitro precursors, be chiral. The chiral conformation of the diamine precursor is maintained in the octahedral zinc(II) and cobalt(II) complexes prepared from the Schiff base. The crystal structures of [ZnL(NO3)(H2O)]NO3 and CoLCl2 complexes exhibit non-planar cis-α configurations with both enantiomers (Δ and Λ). This implies that in the Schiff base ligand the two α-diimine systems shape an octahedral cavity having the same chirality of the precursory diamine. © 2014 Académie des sciences.
Khorshidifard, M. ,
Amiri rudbari, H. ,
Askari, B. ,
Sahihi, M. ,
Farsani, M.R. ,
Jalilian, F. ,
Bruno, G. Publication Date: 2015
Polyhedron (02775387) 95pp. 1-13
An asymmetric bidentate Schiff-base ligand (HL: 2-tert-butyliminomethyl-phenol) was prepared from the reaction of salicylaldehyde and tert-butylamine. Cobalt(II), copper(II), zinc(II) and Pd(II) complexes, CoL2, CuL2, ZnL2 and PdL2, were synthesized from the reaction of CoCl2·6H2O, CuCl2·2H2O, Zn(NO3)2·6H2O and PdCl2 with the bidentate Schiff base ligand HL in methanol. The ligand and its metal complexes were characterized by elemental analysis (CHN), FT-IR and UV-Vis spectroscopy. In addition, 1H and 13C NMR techniques were employed for characterization of the ligand (HL) and the diamagnetic complexes (ZnL2 and PdL2). The molecular structures of all the complexes were determined by the single crystal X-ray diffraction technique. The crystallographic data reveal that in all the complexes the metal centers are four-coordinated by two phenolate oxygen and two imine nitrogen atoms of two Schiff base ligands. The geometry around the metal center in the CoL2, CuL2 and ZnL2 complexes is a distorted tetrahedral and for PdL2 it is square-planar. The catalytic activity of these complexes has been evaluated for the selective oxidation of sulfides with the green oxidant 35% aqueous H2O2 under solvent free conditions. For all the catalysts, using optimized reaction conditions, different sulfides were converted to the corresponding sulfones. ZnL2 showed a higher catalytic performance for the oxidation of the different sulfides to the corresponding sulfones. © 2015 Elsevier Ltd. All rights reserved.
Publication Date: 2015
Applied Organometallic Chemistry (02682605) 29(1)pp. 7-11
The catalytic performance of tetra-n-butylammonium salts of Keggin and Wells-Dawson sandwich-type polyoxotungstates, [M4 (PW9O34)2]m- and [M4(P2W15O56)2]n- (M = Mn2+, Fe3+, Co2+, Ni2+, Zn2+), in the oxidation of cyclooctene and cyclohexene with 30% hydrogen peroxide under various conditions was investigated. In comparison, Wells-Dawson sandwich-type polyoxometalates were found to be less active than Keggin ones. In both of them, those containing Zn and Fe gave higher conversions for different oxidation conditions. These catalysts showed very good reusability in the oxidation reaction. Copyright © 2014 John Wiley & Sons, Ltd.
Bruno, G. ,
Lanza, S. ,
Giannetto, A. ,
Saccá, A. ,
Amiri rudbari, H. ,
Smith g., Publication Date: 2015
Acta Crystallographica Section E: Structure Reports Online (16005368) 71(2)
In the centrosymmetric dinuclear title compound, [Pd2(C4H7)2(C16H14N2S2)], the metal atom is η3-coordinated by three C atoms of a crotyl ligand [Pd - C = 2.147 (4), 2.079 (5) and 2.098 (5) Å], the longest distance influenced by the steric interaction with the benzyl substituents of the dibenzyldithiooximidate (DTO) ligand. The Pd - N and Pd - S bonds to this ligand are 2.080 (3) and 2.3148 (9) Å, respectively, completing a square-planar coordination environment for PdII. The benzyl groups are oriented so as to maximize the interaction between a benzylic H atom and an S atom, resulting in a dihedral angle of 77.1 (2)° between the benzene rings and the metal complex plane. In the crystal, no inter-complex hydrogen-bonding interactions are present.
Giannetto, A. ,
Lanza, S. ,
Bruno, G. ,
Nicolò, F. ,
Amiri rudbari, H. ,
Harrison w.t.a., Publication Date: 2015
Acta Crystallographica Section E: Structure Reports Online (16005368) 71(2)
Two half molecules of the title compound, C16H16N2S2, are present in the asymmetric unit and both molecules are completed by crystallographic inversion centers at the midpoints of the central C - C bonds: the lengths of these bonds [1.538 (5) and 1.533 (5) Å] indicate negligible electronic delocalization. The trans-dithiooxamide fragment in each molecule is characterized by a pair of intramolecular N - H⋯S hydrogen bonds. In the crystal, molecules are linked by weak C - H⋯πs interactions, generating a three-dimensional network.
Imani, N. ,
Behzad, M. ,
Amiri rudbari, H. ,
Bruno, G. ,
Jahromi, H.S. ,
Khaleghian, A. Publication Date: 2015
Journal of Coordination Chemistry (10290389) 68(13)pp. 2296-2306
Two new and two previously reported Schiff base ligands as well as four corresponding new Cu(II) complexes (CuL1-4) were synthesized and characterized. The Schiff base ligands were synthesized from condensation of 5-bromo-2-hydroxy-3-nitrobenzaldehyde with aliphatic (H2L1-2) or aromatic (H2L3-4) diamines. Crystal structures of CuL2 and CuL3 were determined by X-ray crystallography. Antibacterial properties of these ligands and complexes were studied against four human pathogenic bacteria. The complexes showed moderate antibacterial activities, higher than those of the ligands. © 2015 Taylor & Francis.
Behnamfar, M.T. ,
Hadadzadeh h., H. ,
Simpson, J. ,
Darabi, F. ,
Shahpiri, A. ,
Khayamian, T. ,
Ebrahimi, M. ,
Amiri rudbari, H. ,
Salimi, M. Publication Date: 2015
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy (13861425) 134pp. 502-516
Two mononuclear iron complexes, [Fe(tppz)2](PF6) 2·H2O (1) and Fe(tppz)Cl3· 2CHCl3 (2) where tppz is (2,3,5,6-tetra(2-pyridyl)pyrazine), have been synthesized and characterized by elemental analysis, spectroscopic methods (UV-Vis and IR) and single crystal X-ray structure analysis. The interaction of (1) as the nitrate salt ([Fe(tppz)2](NO3)2) with calf-thymus DNA (CT-DNA) has been monitored by UV-Vis spectroscopy, competitive fluorescence titration, circular dichroism (CD), voltammetric techniques, viscosity measurement, and gel electrophoresis. Gel electrophoresis of DNA with [Fe(tppz)2](NO3)2 demonstrated that the complex also has the ability to cleave supercoiled plasmid DNA. The results have indicated that the complex binds to CT-DNA by three binding modes, viz., electrostatic, groove and partial insertion of the pyridyl rings between the base stacks of double-stranded DNA. Molecular docking of [Fe(tppz) 2](NO3)2 with the DNA sequence d(ACCGACGTCGGT)2 suggests the complex fits into the major groove. The water-insoluble complex (2) can catalyze the cleavage of BSA at 40 °C. There are no reports of the catalytic effect of polypyridyl metal complexes on the BSA cleavage. Molecular docking of (2) with BSA suggests that, when the chloro ligands in the axial positions are replaced by water molecules, the BSA can interact with the Fe(III) complex more easily. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2015
Journal Of The Iranian Chemical Society (1735207X) 12(7)pp. 1207-1212
Abstract In this work it was demonstrated that the sodium and potassium salts of a sandwich-type tetra-cobalt tungstophosphate, [Co4(H2O)2(PW9O34)2]10-, are efficient catalysts for the selective oxidation of alcohols into corresponding aldehydes with hydrogen peroxide in water. Among these two salts, Na10[Co4(H2O)2(PW9O34)2]·27H2O complex showed better catalytic activity for the alcohols' oxidation. Using trace amounts of catalyst, different benzylic and aliphatic hydroxyl groups were converted into the corresponding carbonyl compounds in high to excellent yields. Graphical Abstract: In this work green and efficient catalytic oxidation of various alcohols to aldehydes and ketons with a sandwich-type tetra-cobalt tungstophosphate, [Co4(H2O)2(PW9O34)2]10-, is developed. High-to-excellent yields for oxidation of different alcohols by hydrogen peroxide in water are some advantageous of this catalytic system. © 2015 Iranian Chemical Society.
Publication Date: 2015
Inorganica Chimica Acta (18733255) 438pp. 196-202
Five silver(I) compounds namely, [Ag(tdmpp)(NO3)]n (1), [Ag2(SeCN)2(tdmpp)]n (2), [Ag(tdmpp)]PF6 (3), [WS4Ag3Cl (tdmpp)1.5]·2CH3CN (4) and [WS4Ag4I2(tdmpp)]1.5CH3CN (5) were prepared by the reactions of 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane (tdmpp) with various silver(I) salts in order to investigate the impact of the variation of the inorganic anions on the structure of these complexes. In the chain structures of 1 and 2, each tdmpp ligand acts as a bridge between a pair of adjacent silver(I) centers. In the structure of 1, the nitrate ion act as a terminal, monodentate ligand, while in compound 2 the SeCN anion functions as bidentate-bridging ligand between two neighboring Ag(I) centers. The parallel adjacent chains in 1 and 2 are linked together by means of non-covalent interactions to generate two-dimensional structures. In contrast to the distorted AgN4O square-pyramidal structure of 1, in the structure of 2 each of the silver ions possesses a distorted tetrahedral with an AgN3Se coordination geometry. Crystals of compounds 3-5 were not suitable for X-ray diffraction studies. © 2015 Elsevier B.V. All rights reserved.
Beheshti, A. ,
Nobakht, V. ,
Karimi behbahanizadeh, S. ,
Abrahams, C.T. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2015
Inorganica Chimica Acta (18733255) 437pp. 20-25
Three new coordination compounds {[MoOS3Cu3I(bbd)1.5]·2DMF}n (1), {[MoS4Cu3Br(bbd)1.5]·MeOH·2H2O}n (2) and {[WS4Cu3Br(bbd)1.5]·DMF}n (3), incorporating tetranuclear cubane-like cluster units, have been prepared under ambient conditions in DMF by the reaction of CuX (X = Br, I) and (NH4)2[MXS3] (M = Mo, W; X = S, O) with a flexible linker ligand, 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd). The complexes have been characterized by elemental analyses, IR and UV-Vis spectroscopy. Single-crystal X-ray structure determinations of 1 and 2 have also been undertaken. In the polymeric structures of 1 and 2, two inorganic tetranuclearcubane-like fragments [MoOS3Cu3I] (in 1) and [MoS4Cu3Br] (in 2) are linked by a pair of μ-bbd ligands to form 22-membered rings. In both polymers, the double-cluster/double-bridge units are further linked by a single μ-bbd ligand to generate polymeric chains. In 1 and 2 the Cu atoms possess a distorted tetrahedral geometry formed by an S2NX donor atom set (X = I in 1 and X = Br in 2). In 1, adjacent chains are stabilized by intermolecular C-Ha⋯π interactions. © 2015 Elsevier B.V.
Yousef ebrahimipour s., S.Y. ,
Sheikhshoaie, I. ,
Kautz, A.C. ,
Ameri, M. ,
Pasban-aliabadi, H. ,
Amiri rudbari, H. ,
Bruno, G. ,
Janiak, C. Publication Date: 2015
Polyhedron (02775387) 93pp. 99-105
Three oxido-vanadium(V) complexes, [VO2(L)][NH(Et)3] (1), [VO(L)(PrO)] (2) and [VO(L)(BuO)] (3), containing deprotonated form of the tridentate Schiff base ligand 1-(((5-chloro-2-oxidophenyl)imino)methyl)naphthalen-2-olate [L2-] have been synthesized and characterized using elemental analysis, molar conductivity, FTIR, 1H NMR analysis, and electronic spectroscopy. The structures of the free H2L ligand and all the complexes were determined by single crystal X-ray diffraction. According to the spectroscopic and structural data, H2L exists in the solid state in a zwitterionic form. In all the complexes, the V(V) center is coordinated by the ONO donor set of the L2- ligand, one or two oxido groups and in the case of 2 and 3 by one alkoxide group (PrO- for 2 and BuO- for 3) in a distorted square pyramidal geometry. The anticancer activities of the title complexes have been also investigated against MCF-7 (breast cancer) cells and compared with that of VO(acac)2. According to the obtained results, all the complexes possess higher anticancer activity than VO(acac)2. © 2015 Elsevier Ltd. All rights reserved.
Publication Date: 2015
Polyhedron (02775387) 100pp. 180-191
A new unsymmetrical Schiff base ligand (H2L) was derived from the 1:1 M condensation of 2,3-dihydroxybenzaldehyde with allylamine. Molybdenum(VI) complex, MoO2L2, was synthesized from the reaction of MoO2(acac)2 with the Schiff base ligand in a 1:2 ratio in methanol at ambient temperature. The Schiff base ligand and its Mo(VI) complex were characterized by elemental analyses, FT-IR, 1H NMR, 13C NMR and UV-Vis spectroscopies and single crystal X-ray analysis. The molecular structure of schiff base ligand and Mo(VI) complex showed pseudo-scorpionate structure in solid state. The MoO2L2 complex adopts an octahedral environment around the Mo center with a cis-oxo configuration. The other coordination sites are occupied by the hydroxyl oxygen atoms of the two Schiff base ligands. The pseudo-scorpionate interaction in ligand was investigated by theoretical calculation. The Schiff base ligand and its Mo(VI) complex were also tested for their in vitro antimicrobial activity against Staphylococcus aureus (ATCC 29737) and Pseudomonas aeroginosa (PTTC 1570) as examples of Gram-positive and Gram-negative bacterial strains, respectively, by disc diffusion method. The results indicated that the Schiff base ligand had a better antibacterial activity than its Mo(VI) complex and surprisingly, they were synergistic when used against P. aeroginosa PTTC 1570. © 2015 Elsevier Ltd.
Jalilian, F. ,
Yadollahi, B. ,
Farsani, M.R. ,
Tangestaninejad, S. ,
Amiri rudbari, H. ,
Habibi, R. Publication Date: 2015
Catalysis Communications (15667367) 66pp. 107-110
The catalytic activity of three Keplerate polyoxometalates Mo72M30 (M = V, Cr, Fe) was examined in the H2O2-based oxidation of different sulfides in water. Various sulfides were successfully converted into the corresponding sulfones under mild reaction conditions with high to excellent yields. The recyclability of Keplerate POM catalysts did not show a significant loss of catalytic activity up to five times. The use of water and hydrogen peroxide as green solvent and oxidant makes these reactions interesting from environmental and economic points of view. © 2015 Elsevier B.V. All rights reserved.
Publication Date: 2015
Organic Letters (15237052) 17(19)pp. 4666-4669
A regioselective green synthesis of nitroacetaminophen derivatives was carried out by electrochemical oxidation of acetaminophen, N-(2-hydroxyphenyl)acetamide, and 1-(4-(4-hydroxyphenyl)piperazin-1-yl)ethanone in the presence of nitrite ion as a nucleophile. The present work has led to the development of a reagentless green and facile electrochemical method for the synthesis of some nitroacetaminophen derivatives. © 2015 American Chemical Society.
Yousef ebrahimipour s., S.Y. ,
Mohamadi, M. ,
Castro, J. ,
Mollania, N. ,
Amiri rudbari, H. ,
Saccá, A. Publication Date: 2015
Journal of Coordination Chemistry (10290389) 68(4)pp. 632-649
Two mixed-ligand complexes, [Cu(L)(2imi)] (1) and [Ni(L)(2imi)]•MeOH (2) [L = 2-(((5-chloro-2-oxyphenyl)imino)methyl)phenolato) and 2imi = 2-methyl imidazole], have been prepared by the reaction of appropriate metal salts with H2L and 2-methyl imidazole. Their structures were characterized by microanalysis, FT-IR, UV-vis, molar conductivity, and 1H NMR for [Ni(L)(2imi)]•MeOH. The structures were determined using single crystal X-ray diffraction. Each four-coordinate metal center, Cu(II) in 1 and Ni(II) in 2, is surrounded by donors of Schiff base (L2-) and N of 2-methyl imidazole in square planar geometries. α-Amylase activities of these compounds have also been investigated. The experimental data showed that α-amylase was inhibited by Ni(II) complex while the Cu(II) complex causes a 1.3-fold decrease in Km value. Antimicrobial results show that these compounds, especially the Cu(II) complex, have potential for antibacterial activity against Gram negative and Gram positive bacteria and antifungal activity against Aspergillus fumigatus. © 2015 Taylor & Francis.
Molaei, F. ,
Bigdeli, F. ,
Morsali, A. ,
Joo, S.W. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2015
Journal of Molecular Structure (00222860) 1095pp. 8-14
Two new zinc(II) coordination polymers, [Zn(Quinoxaline)(NO3)2(H2O)2]n·Quinoxaline·H2O (1) and [Zn(Quinoxaline)2(Br)2]n (2), Quinoxaline = Benzopyrazine, have been synthesized and characterized by IR spectroscopy. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and are one-dimensional coordination polymers with coordination environment of octahedral and tetrahedral respectively. Nanostructures of zinc(II) oxide were obtained by thermolyses of compound 1 in oleic acid, calcination of compound 1 at 500 °C under air atmosphere and sol-gel processes. Also, nanopowders of zinc(II) oxide were obtained by calcination of compound 2 at 450 and 550 °C. The nanomaterials were characterized by scanning electron microscopy and X-ray powder diffraction (XRD). The thermal stability of compounds 1 and 2 both their bulk were studied by thermo-gravimetric (TGA) and differential thermal analyses (DTA). This study demonstrates the coordination polymers may be suitable precursors for the preparation of nanoscale materials. © 2015 Elsevier B.V. All rights reserved.
Keypour, H. ,
Zeynali, H. ,
Rezaeivala, M. ,
Mohsenzadeh, F. ,
Amiri rudbari, H. ,
Bruno, G. ,
Sadeghpour, A. Publication Date: 2015
Journal Of The Iranian Chemical Society (1735207X) 12(9)pp. 1665-1675
Four macrocyclic Schiff base ligands (L1, L2, L3, and L4) have been prepared. In the presence of Copper(II), original macrocycles were converted to the three new binuclear polymeric complexes [Cu2L 2 1′ ](NO3)2, [Cu2L 2 2′ ](NO3), and [Cu2L 2 3′ ](NO3)2. But in the presence of Nickel(II), macrocyclic rings remained unchanged and Schiff base complexes of [NiL1(CH3CN)2(CH3OH)2](ClO4)2 and [NiL4](NO3)2 were synthesized. All ligands and their related complexes were characterized by elemental analysis, IR spectroscopy, in the case of ligands 1H, 13C NMR and EI-Mass and for [Cu2L2′](NO3)2 and [NiL1(CH3CN)2(CH3OH)2](ClO4)2 complexes X-ray crystal structure determination have been performed. Crystal structure showed 1D zigzag polymer for [Cu2L 2 1′ ](NO3)2 and macrocyclic structure for [NiL1(CH3CN)2(CH3OH)2](ClO4)2 complexes. The ligands and related polymeric complexes were screened for their antibacterial activities against six bacterial strains and the complexes showed antibacterial effects. © 2015 Iranian Chemical Society.
Publication Date: 2015
Journal of Inorganic and Organometallic Polymers and Materials (15741443) 25(5)pp. 1032-1039
Three new mercury(II) coordination monomers, HgLX3 [X = Cl− (1) and Br− (2)], and polymer, [HgLI2]n, (3), L = 5-methyl-5-(3-pyridyl)-2,4-imidazolidenedione, have been synthesized and characterized by elemental analysis (C, H, and N %) and flame atomic absorption (Hg %), IR, and NMR spectroscopy. Complexes 1 and 2 have the same framework structure while the structure of complex 3 is an infinite 2D layers. According to X-ray diffraction analysis, complex 3 crystallizes in monoclinic system. In this polymeric complex, [Hg(C9H9N3O2)I(μ-I)2]n, HgII atom is coordinated by one L and three I− anions with a distorted tetrahedral geometry; one I− anion is in a monodentate coordination mode and the other two are bridging, linking HgII atoms into a one-dimensional chain. Classical hydrogen-bonding interactions (O···H–N) between adjacent ligands result in a zigzag type arrangement of one chain while consecutive polymeric chains are linked by non-classical ones (O···H–C) to form 2D supramolecular layers. The results indicate that the flexible ligand can form complexes with varied structures. In addition, the species of the halide were found to have great impact on the structure of the complexes. Antibacterial activity of L and the corresponding complexes investigated against six species of microorganisms. Testing was performed by disk diffusion method, and minimum inhibitory concentrations have been determined. Noteworthy antimicrobial activities for these complexes were observed. © 2015, Springer Science+Business Media New York.
Publication Date: 2015
Transition Metal Chemistry (1572901X) 40(7)pp. 715-722
A potentially hexadentate N4O2 Schiff base ligand, L, has been synthesized by condensation of an aromatic diamine with 2-pyridinecarbaldehyde. The complexes [MLNO3]NO3 (M=Cu, Ni, Cd or Zn) and [MlCl2] (M=Co or Mn) were synthesized by the reactions of L with metal salts in methanol. Both free L and its complexes were characterized by physicochemical and spectroscopic methods. In addition, the crystal structures of [CuLNO3]NO3 and [ZnLNO3]NO3 have been determined by single-crystal X-ray diffraction. In both complexes, the ligand L is coordinated via pyridine and azomethine nitrogen atoms to give a distorted octahedral geometry. These complexes have antibacterial activities against three Gram-positive and three Gram-negative bacteria, which in most cases exceed those of tobramycin and tetracycline as standards. © 2015 Springer International Publishing Switzerland 2015.
Beheshti, A. ,
Lalegani, A. ,
Behvandi, F. ,
Safaeiyan, F. ,
Sarkarzadeh, A. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2015
Journal of Molecular Structure (00222860) 1082pp. 143-150
(Chemical Equation Presented). Four new complexes of [Hg2Cl4(bpp)]n (1), [Hg2Cl4(tdmpp)] (2), [Cd2I4(tdmpp)] (3) and [Fe2Cl4(tdmpp)] (4) were prepared by using the neutral N-donor ligands 1,3-bis(3,5-dimethyl-1-pyrazolyl)propane (bpp) and 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl)propane (tdmpp) with different flexibility and appropriate metal salts of Cd(II), Hg(II) and Fe(II) ions. These compounds were characterized by the infrared spectroscopy, elemental analysis and X-ray crystallography. Flexible ligands and non-covalent C-H⋯Cl hydrogen bonds play a major role in the crystal packing of compounds 1, 2 and 4. In the two-dimensional non-covalent structure of 1, there are two distinctly different coordination modes for the mercury atoms. One mercury atom has pseudo-trigonal bipyramidal geometry and the other adopts a distorted tetrahedral environment. In the dinuclear structures of 2 and 4 the neutral molecules are linked together by the C-H⋯Cl hydrogen bonds, forming an infinite one-dimensional zigzag chain structure. Compounds 2-4 are isostructural with each other. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2015
Polyhedron (02775387) 97pp. 75-82
Abstract Two new hexadentate N2O4 Schiff base ligands, H2L1 and H2L2, from condensation of 2-(2-((2-aminophenoxy)methyl)benzyloxy)benzenamine with 2-hydroxybenzaldehyde or 2-hydroxy-3-methoxybenzaldehyde, respectively have been prepared. From direct reaction of these ligands and Cu(II), Co(II), Ni(II) and Cd(II) metal salts in methanolic solution, the neutral [CuL1], [CoL1], [NiL1], [CdL1], [ZnL1], [CuL2], [CoL2], [NiL2], [CdL2] and [ZnL2] complexes were synthesized. These ligands and their complexes were characterized by elemental analysis, spectroscopic methods (UV-Vis, 1H, 13C NMR, EI-MS and IR). The conductivity data confirm the non-electrolytic nature of the all complexes. Also the crystal structure of [ZnL1], [NiL2] and [CoL2] complexes have also been determined by X-ray crystallographic technique. The Zn(II), Ni(II) and Co(II) complexes show a distorted octahedral configuration. The synthesized complexes have antibacterial activity against the three Gram-positive bacteria: Staphylococcus aureus, Enterococcus faecalis and Bacillus cereus and against the three Gram-negative bacteria: Escherichia coli, Proteus vulgaris and Pseudomonas aeruginosa and also against two yeast: Candida tropicalis and Candida albicans. The results showed that in some cases the antibacterial activity of complexes were more than Tetracycline and Natamycin as standards. The cleavage of DNA by all synthesized complexes were examined using gel electrophoresis experiments. The results showed that both of the Cu(II) complexes (except for 78 μM [CuL1] complex) were completely broken structure of form I and form II DNA at all concentrations tested. © 2015 Published by Elsevier Ltd.
Publication Date: 2015
Journal of Molecular Structure (00222860) 1081pp. 494-505
An asymmetric bidentate Schiff-base ligand (HL: 2-((allylimino)methyl)phenol) was prepared from reaction of salicylaldehyde and Allylamine. Vanadium(IV), Cobalt(III), Copper(II) and Zinc(II) complexes, VOL2, CoL3, CuL2 and ZnL2 were synthesized from the reaction of VO(acac)2, CoCl2·6H2O, CuCl2·2H2O and Zn(NO3)2·6H2O with the bidentate Schiff base ligand (HL: 2-allyliminomethyl-phenol) in methanol at ambient temperature. The ligand and its metal complexes were characterized by elemental analysis (CHN), FT-IR spectroscopy. In addition, 1H and 13C NMR techniques were employed for characterization of the ligand (HL) and diamagnetic complex ZnL2. The molecular structures of all complexes were determined by single crystal X-ray diffraction technique. In the ZnL2 and CuL2 complexes, the metal ion is coordinated by two nitrogen and two oxygen atoms from two Schiff base ligands in an approximately square planar trans-[MN2O2] coordination geometry. In the Vanadium(IV) complex, VOL2, the vanadium center in this structure has a distorted tetragonal pyramidal N2O3 coordination sphere and for Cobalt(III) complex, CoL3, the CoIII ion is six coordinated by three bidentate Schiff base ligands in a distorted octahedral environment. © 2014 Elsevier B.V. All rights reserved.
Kazemi, Z. ,
Amiri rudbari, H. ,
Mirkhani, V. ,
Sahihi, M. ,
Moghadam, M. ,
Tangestaninejad, S. ,
Mohammadpoor baltork, I. Publication Date: 2015
Journal of Molecular Structure (00222860) 1096pp. 110-120
(Chemical Presented) A tridentate Schiff base ligand NNO donor (HL: 1-((E)-((pyridin-2-yl)methylimino)methyl)naphthalen-2-ol was synthesized from condensation of 2-hydroxynaphtaldehyde and 2-picolylamine. Zinc complex, Zn2L2(NO3)2, was prepared from reaction of Zn(NO3)2 and HL at ambient temperature. The ligand and complex were characterized by FT-IR, 1H NMR, 13C NMR and elemental analysis (CHN). Furthermore, the structure of dinuclear Zn(II) complex was determined by single crystal X-ray analysis. The complex, Zn2L2(NO3)2, is centrosymmetric dimer in which deprotonated phenolates bridge the two Zn(II) atoms and link the two halves of the dimer. In the structure, Zinc(II) ions have a highly distorted six-coordinate structure bonded to two oxygen atoms from a bidentate nitrate group, the pyridine nitrogen, an amine nitrogen and phenolate oxygens. The interaction of dinuclear Zn(II) complex with fish sperm DNA (FS-DNA) and HSA was investigated under physiological conditions using fluorescence quenching, UV-Vis spectroscopy, molecular dynamics simulation and molecular docking methods. The estimated binding constants for the DNA-complex and HSA-complex were (3.60 ± 0.18) × 104 M-1 and (1.35 ± 0.24) × 104 M-1, respectively. The distance between dinuclear Zn(II) complex and HSA was obtained based on the Förster's theory of non-radiative energy transfer. Molecular docking studies revealed the binding of dinuclear Zn(II) complex to the major groove of FS-DNA and IIA site of protein by formation of hydrogen bond, π-cation and hydrophobic interactions. © 2015 Elsevier B.V. All rights reserved.
Farzanfar, J. ,
Ghasemi, K. ,
Rezvani, A.R. ,
Delarami, H.S. ,
Ebrahimi, A. ,
Hosseinpoor, H. ,
Eskandari, A. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2015
Journal of Inorganic Biochemistry (01620134) 147pp. 54-64
Three new thiourea ligands derived from the condensation of aroyl- and aryl-isothiocyanate derivatives with 2,6-diaminopyridine, named 1,1′-(pyridine-2,6-diyl)bis(3-(benzoyl)thiourea) (L1), 1,1′-(pyridine-2,6-diyl)bis(3-(2-chlorobenzoyl)thiourea) (L2) and 1,1′-(pyridine-2,6-diyl)bis(3-(4-chlorophenyl)thiourea) (L3), their oxido-vanadium(IV) complexes, namely [VO(L1')(H2O)] (C1), [VO(L2')(H2O)] (C2) and [VO(L3')(H2O)] (C3), and also, dioxo-vanadium(V) complex containing 4-hydroxy-2,6-pyridine dicarboxylic acid (chelidamic acid, H2dipic-OH) and metformin (N,N-dimethylbiguanide, Met), named [H2Met][VO2(dipic-OH)]2·H2O (C4), were synthesized and characterized by elemental analysis, FTIR and 1H NMR and UV-visible spectroscopies. Proposed structures for free thiourea ligands and their vanadium complexes were corroborated by applying geometry optimization and conformational analysis. Solid state structure of complex [H2Met][VO2(dipic-OH)]2·H2O (triclinic, Pi¯) was fully determined by single crystal X-ray diffraction analysis. In this complex, metformin is double protonated and acted as counter ion. The antibacterial properties of these compounds were investigated in vitro against standard Gram-positive and Gram-negative bacterial strains. The experiments showed that vanadium(IV) complexes had the superior antibacterial activities than novel thiourea derivatives and vanadium(V) complex against all Gram-positive and Gram-negative bacterial strains. © 2015 Elsevier Inc. All rights reserved.
Sheikhshoaie, I. ,
Yousef ebrahimipour s., S.Y. ,
Sheikhshoaie, M. ,
Mohamadi, M. ,
Abbasnejad, M. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2015
Journal Of Chemical Sciences (09743626) 127(12)pp. 2193-2200
A ternary mixed ligand Cu(II) complex, [Cu(L)(Phen)], was prepared from the reaction of (E)-N′-((2-hydroxynaphthalen-1-yl)methylene)acetohydrazide [HL], Cu(NO3)2.3H2O and 1,10-Phenanthroline in 1:1:1 molar ratio. This complex was fully characterized using spectroscopic and physicochemical methods. The structure of the complex was determined by single crystal X-ray diffraction. The Cu(II) center is coordinated by two oxygen and one nitrogen donors of L2- and nitrogen atoms of the heterocyclic group. Electrochemical studies of the Cu(II) complex showed shifts in the ligand peaks as well as the appearance of new peaks after complexation. The electrochemical behavior of the Cu(II) complex was also studied using cyclic voltammetry. According to biochemical investigation (MCF-7 cells viability), anticancer activity of [Cu(L)(Phen)] was higher than those of Cu(NO3)2.3H2O, HL and 1,10-Phenanthroline. © 2015 Indian Academy of Sciences.
Publication Date: 2015
Polyhedron (02775387) 85pp. 690-696
Two new coordination compounds, [Cu(μ-bbd)(NCS)2]n (1) and [Cu2Cl4(μ-tdmpp)(H2O)2] (2), were prepared at room temperature by the reaction of CuX2 (X = Cl, SCN) salts with the flexible linker ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,1,3,3-tetrakis(3,5-dimethypyrazol-1-yl)propane (tdmpp). The complexes were characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. In the polymeric structure of 1, the copper(II) ion lies on a center of symmetry within a square-planar trans-CuN4 coordination geometry. The NCS groups are terminally N-bonded to the metal center and the μ-bbd ligand, with a gauche-anti-gauche conformation, acts as a centrosymmetric bridging bidentate ligand, linking the Cu(II) centers into a one-dimensional zigzag chain structure. In contrast to 1, complex 2 has a dinuclear structure in which each of the copper(II) ions is five-coordinated in a distorted CuN2Cl2O square-based pyramidal coordination geometry. The neighboring discrete [Cu2Cl4(μ-tdmpp).(H2O)2] molecules are connected by intermolecular O-HCl hydrogen bonds to form an infinite chain of neutral molecules. The adjacent 1D chains of complex 2 are further extended into a non-covalent 3D network structure by C-HO intermolecular hydrogen bonds. The polymeric structure of [Cu(CH3CN)(μ3-SCN)]n (3) was obtained as an unexpected product in an attempt to synthesize the [Cu(μ-bpp)(SCN)2]n polymer in acetonitrile solution. © 2014 Elsevier Ltd. All rights reserved.
Publication Date: 2015
Inorganic Chemistry Communications (13877003) 59pp. 41-45
Abstract In this paper, the Zn-based analogue of Cu3(btc)2 (HKUST-1), Zn3(btc)2 nanorods (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) have been synthesized through direct precipitation in solution phase under ultrasound condition without the assistance of any surfactant, catalyst, or template. Zn-HKUST-1 nanorods werecharacterized by Fourier transform infrared studies, elemental analysis, powder X-ray diffraction and field emission scanning electron microscopy. Concentration of initial reagent effects on size and morphology of the Zn-HKUST-1 has been studied and shows that low concentrations of initial reagents decreased widths, thicknesses, and lengths of nanorods. Subsequently, ligand-free ZnO nanorods and nanoparticles are selectively prepared via a thermal decomposition method using the corresponding nanorods and single crystals as a precursor, respectively. This solid-state transformation route is promising for the preparation of crystalline nanomaterials with desired morphologies because of its simplicity and the low cost of the starting reagents. © 2015 Published by Elsevier B.V.
Publication Date: 2014
Polyhedron (02775387) 76pp. 102-107
The tetra-n-butylammonium (TBA) salts of Keggin and Wells-Dawson sandwich type polyoxotungstates, [M4(PW9O34) 2]m- and [M4(P2W 15O56)2]n- (M = Mn 2+, Fe3+, Co2+, Ni2+ and Zn 2+), proved to be effective catalysts for the oxidation of benzylic alcohols to the corresponding aldehydes with 30% hydrogen peroxide in acetonitrile. The Wells-Dawson type polyoxometallates showed lower activity than the Keggin ones, and both the Zn substituted polyoxometallates depicted higher conversions. Oxidation of different benzylic alcohols with electron withdrawing and electron donating substituents gave high to excellent yields in the presence of Zn substituted POMs. © 2014 Elsevier B.V. All rights reserved.
Farrokhpour h., H. ,
Hadadzadeh h., H. ,
Darabi, F. ,
Abyar, F. ,
Amiri rudbari, H. ,
Ahmadi-bagheri, T. Publication Date: 2014
RSC Advances (20462069) 4(67)pp. 35390-35404
A rare mononuclear Cu(ii) complex, trans-[Cu(cip)2(OH) 2]·2CH3OH·6H2O, where cip +/- is a zwitterionic form (+H2N-⋯- COO-) of ciprofloxacin, has been synthesized and characterized by spectroscopic methods and X-ray crystallography. In vitro studies (UV-Vis spectroscopy, emission titration, voltammetric techniques, and gel electrophoresis) show that the complex interacts with calf-thymus DNA (CT-DNA) via an intercalative binding mode. The microenvironment and the secondary structure of BSA are changed in the presence of the complex. Also, our Own N-layered Integrated molecular Orbital and molecular Mechanics (ONIOM) method, based on the hybridization of QM/MM methodology, was carried out to investigate the interaction of the complex with DNA and BSA. The calculated electronic interaction energy of the complex with DNA in the gas phase and water is -64.358 and -56.685 kcal mol-1, respectively. The calculated interaction of the complex with BSA is -54.231 kcal mol-1. The theoretical data confirm the experimental results with respect to the mechanism of binding and binding constants. Finally, the calculations indicate that the QM/MM is a more precise method than the docking method for determination of the electronic interaction energies because of two reasons: (I) it considers the complex quantum mechanically in calculations, and (II) it accounts for the polarization of the wave function of the complex by the charge distribution of the molecular mechanical part (DNA and BSA). © 2014 the Partner Organisations.
Takjoo, R. ,
Ramasami, P. ,
Hashemzadeh, A. ,
Rhyman, L. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2014
Journal of Coordination Chemistry (10290389) 67(8)pp. 1392-1404
Two nickel(II) isothiosemicarbazone complexes of dianionic 5-bromosalicylaldehyde S-allyl isothiosemicarbazonehydrobromide (H 2L.HBr), [Ni(Im)L] and [Ni(2-MeIm)L] (Im: imidazole, 2-MeIm: 2-methylimidazole), were synthesized and characterized by single crystal X-ray crystallography, 1H NMR spectrometry, IR, and electronic spectroscopy. The complexes have square-planar geometry and the ligand is coordinated as a dinegative tridentate chelating agent via phenolic oxygen, isothioamide nitrogen, and azomethine nitrogen atoms. To complement the experimental data, density functional theory (DFT) and time-dependent DFT methods were used to validate the structural parameters and infrared and electronic spectra. © 2014 Taylor and Francis.
Sanatkar, T.H. ,
Hadadzadeh h., H. ,
Jannesari, Z. ,
Khayamian, T. ,
Ebrahimi, M. ,
Amiri rudbari, H. ,
Torkzadeh-mahani, M. ,
Anjomshoa, M. Publication Date: 2014
Inorganica Chimica Acta (18733255) 423(PB)pp. 256-272
Two complexes of Cu(II) and Ni(II) with the non-steroidal anti-inflammatory drug meloxicam (H2mel, 4-hydroxy-2-methyl-N-(5-methyl-2-thiazolyl)-2H-1,2-benzothiazine-3-carboxammide-1,1-dioxide), trans-[Cu(Hmel)2(THF)2] (1) and trans-[Ni(Hmel)2(DMF)2] (2), were synthesized and characterized. The interaction of the complexes with DNA and bovine serum albumin (BSA) was investigated. Molecular docking and molecular dynamic simulation methods were also used for modeling the binding of the complexes to DNA and BSA and good agreements were found between the experimental and theoretical results. All the results suggest that the interaction mode between the complexes and DNA was major groove binding. The quenching mechanism of the BSA fluorescence by the complexes is a static quenching. Gel electrophoresis assay demonstrates the ability of the complexes to cleave the supercoiled plasmid DNA (pUC57 plasmid DNA). © 2014 Elsevier B.V. All rights reserved.
Sheikhshoaie, I. ,
Yousef ebrahimipour s., S.Y. ,
Sheikhshoaie, M. ,
Amiri rudbari, H. ,
Khaleghi, M. ,
Bruno, G. Publication Date: 2014
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy (13861425) 124pp. 548-555
A Schiff base ligand, 2-hydroxyacetophenone benzoylhydrazone (HL) was synthesized and fully characterized with FT-IR, elemental analyses, UV-Vis, H-1 NMR and C-13 NMR spectra. DFT calculations using B3LYP/6-31+G(d,p) and PW91/DZP are performed to optimize the molecular geometry. Optimized structures are used to calculate FT-IR, UV-Vis, H-1 NMR and C-13 NMR spectra of the compound. Also the energies of the frontier molecular orbitals (FMOs) have been determined. The results obtained from the optimization and spectral analyses are in good agreement with the experimental data. To investigate non-linear optical properties, the electric dipole moment (mu), polarizability (alpha) and molecular first hyperpolarizability (beta) were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the compound can be a good candidate of nonlinear optical materials. In addition, the minimal inhibitory concentration (MIC) of this compound against Staphylococcus aureus, and Candida albicans was determined. (C) 2014 Elsevier B.V. All rights reserved.
Haghighi, F.H. ,
Hadadzadeh h., H. ,
Farrokhpour h., H. ,
Serri, N. ,
Abdi, K. ,
Amiri rudbari, H. Publication Date: 2014
Dalton Transactions (14779226) 43(29)pp. 11317-11332
A new mononuclear ruthenium(ii) complex, trans-[Ru(dmb)2(Cl) (EtOH)](PF6) (dmb = 4,4′-dimethyl-2,2′-bipyridine), has been prepared and characterized by elemental analysis, spectroscopic techniques and single crystal X-ray structure determination. The complex was studied as a precatalyst for the electrocatalytic reduction of CO2 to CO in an acetonitrile solution by cyclic voltammetry (CV). The catalytic mechanism was investigated by means of quantum chemical calculations to gain deeper insight into the process of CO2 reduction. The results suggest that the reaction proceeds in six steps initiating by the two sequential 1ē reductions at the dmb ligands followed by CO2 addition to give a metallocarboxylate intermediate. This intermediate undergoes further reduction and loses a CO molecule. The results reported in this paper are of great significance in providing theoretical insight into a class of electrocatalysts for reduction of CO2 to CO. This journal is © the Partner Organisations 2014.
Nasr-esfahani, M. ,
Mohammadpoor baltork, I. ,
Khosropour, A.R. ,
Moghadam, M. ,
Mirkhani, V. ,
Tangestaninejad, S. ,
Agabekov, V. ,
Amiri rudbari, H. Publication Date: 2014
RSC Advances (20462069) 4(27)pp. 14291-14296
A highly efficient route for the synthesis of symmetrical and unsymmetrical 1,3-diynes has been developed by Cu(ii)-TD@nSiO2/DBU catalyzed homocoupling/heterocoupling of aromatic as well as aliphatic terminal alkynes under aerobic conditions at ambient temperature. The catalyst could be easily recovered and reused several times without significant loss of its activity. © 2014 The Royal Society of Chemistry.
Nasr-esfahani, M. ,
Mohammadpoor baltork, I. ,
Khosropour, A.R. ,
Moghadam, M. ,
Mirkhani, V. ,
Tangestaninejad, S. ,
Amiri rudbari, H. Publication Date: 2014
Journal of Organic Chemistry (15206904) 79(3)pp. 1437-1443
An efficient, atom-economical, and regioselective synthesis of a wide range of 1,4-disubstituted 1,2,3-triazoles in excellent yields has been achieved via a one-pot three-component reaction of alkynes and sodium azide with organic halides or α-bromo ketones catalyzed by Cu(II)-TD@nSiO2/sodium ascorbate at room temperature. This catalytic system also showed excellent activity in the synthesis of bis- and tris-1,4-substituted 1,2,3-triazoles. Moreover, the catalyst could be recycled and reused for seven cycles without any loss in its catalytic activity. © 2014 American Chemical Society.
Saljooghi a.s., A.S. ,
Amiri rudbari, H. ,
Nicolò, F. ,
Salimi a., ,
Delavarmendi f., ,
Zahmati m., M. Publication Date: 2014
Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya (10703284) 40(6)pp. 424-431
The Cu(II) complexes [Cu(Tppz)(Dipic)] · 8H2O (I) and [Pb2(Tppz)Cl4] n (II), where Tppz, H2Dipic are 2,3,5,6-tetrakis(2-pyridyl)pyrazine, dipicolinic acid, respectively, have been synthesized and characterized by elemental analyses, IR, cyclic voltammetry, and electronic spectral studies. Solid state structures of both complexes have been determined by single crystal X-ray crystallography. An ORTEP drawing of two complexes shows that the coordination geometry around the metal center is a distorted octahedron. There are extensive conventional intermolecular O-H...O, N-H...O, and weaker C-H...O and C-H...Cl non-classical hydrogen bonds, which cause the stability of the crystal structure. Crystal data for I: monoclinic, space group: C2/c, a = 35.421(3), b = 8.422(6), c = 22.824(8) Å, β = 101.69(2)°, V = 6668(5) Å3, Z = 8. Crystal data for II: triclinic, space group P \bar 1, a = 7.9534(4), b = 8.8682(5), c = 9.4245(5) Å, β = 95.086(2)°, V = 655.93(6) Å3, Z = 2. © 2014 Pleiades Publishing, Ltd.
Publication Date: 2014
Polyhedron (02775387) 76pp. 22-28
The synthesis, structure and spectroscopic properties of a tricarbonylrhenium(I) complex with the N,N′-bis(2-methylbenzaldehyde)-1,2- diiminoethane Schiff base ligand have been investigated. This complex was characterized by FT-IR, NMR, UV-Vis spectroscopy and X-ray crystallography. Optimized geometric parameters and electronic properties of the synthesized compound and some similar Re(I) tricarbonyl complexes were obtained. The low lying electronic transition energies of the complexes have been determined with the time dependent density functional theory method. The calculations showed that in the complexes the HOMOs cover the Re atom, carbonyl groups and chlorine p orbitals, while the LUMOs are mainly localized on the diimine ligand as a π* orbital. © 2014 Elsevier Ltd. All rights reserved.
Publication Date: 2014
Journal of Molecular Structure (00222860) 1063(1)pp. 1-7
Three new nickel(II) complexes of a series of methoxy substituted salen type Schiff base ligands were synthesized and characterized by IR, UV-Vis and 1H NMR spectroscopy and elemental analysis. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with n-methoxysalicylaldehyde (n = 3, 4 and 5). Crystal structures of these complexes were determined. Electrochemical behavior of the complexes was studied by means of cyclic voltammetry in DMSO solutions. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant under various conditions to find the optimum operating parameters. Low catalytic activity with moderate epoxide selectivity was observed in in-solvent conditions but in the solvent-free conditions, enhanced catalytic activity with high epoxide selectivity was achieved. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2014
Journal of Organometallic Chemistry (0022328X) 754pp. 26-31
Four new dinuclear organotin(IV) complexes, (R2Sn) 2La [R = Me (1), R = Ph (2)] and (R2Sn) 2Lb [R = Me (3), R = Ph (4)], have been synthesized from the reaction of R2SnCl2 (R = Me or Ph) with bis(2-hydroxy-3-methoxybenzylidene)succinohydrazide (H4La) and bis(5-bromo-2-hydroxybenzylidene)succinohydrazide (H4L b). The synthesized compounds have been investigated by elemental analysis, IR, 1H NMR, 13C NMR and 119Sn NMR spectroscopy. The results show the all complexes are dinuclear and two doubly deprotonated tridentate domain of the acyldihydrazone is coordinated to two SnR2 moieties via phenolic oxygen, imine nitrogen and enolic oxygen. The structures of 1 and 3 have been also confirmed by X-ray crystallography. Both complexes are centrosymmetry with the alkyl linker chain shows anti conformation. The intermolecular weak SnO bonds lead to 1D polymeric chain containing four-membered Sn2O2 planar rings. On the basis of 119Sn NMR data coordination number of tin is five in solution. © 2013 Elsevier Inc. All rights reserved.
Farsani, M.R. ,
Yadollahi, B. ,
Amiri rudbari, H. ,
Amini, A. ,
Caradoc-davis, T. ,
Price, J.R. Publication Date: 2014
Inorganic Chemistry Communications (13877003) 43pp. 39-44
A stable sandwich type Keggin polyoxometalate, Na4K 5[K3Cu3(NO3)(A-α-PW 9O34)2], has been synthesized and crystallized by a simple reaction method. Elemental analysis, FTIR, UV-vis, X-ray single crystal, thermal gravimetry, and cyclic voltammetry were used for the characterization of synthesized POM. The TBA salt of [K3Cu 3(PW9O34)2]9 - revealed high catalytic activity and 74-99% selectivity in the liquid phase epoxidation of alkenes with aqueous H2O2. The X-ray structure of this complex reveals that three Cu(II) ions are sandwiched between two A-α-PW9O34 moieties and that a nitrate monoanion is encapsulated in the same plane as the three Cu(II) atoms. The nitrate is coplanar with the three copper atoms, which are each in a distorted square-pyramidal environment. After recrystallization, the NO3 - group in the central belt didn't exit, in which this phenomenon is attributed to the type of counterion in the complex (as a result of mixing Na+ and K+ as counterions). This compound showed excellent stability in different pH and also didn't dissociate with hydrogen peroxide. © 2014 Elsevier B.V.
Publication Date: 2014
Inorganica Chimica Acta (18733255) 423(PART A)pp. 101-105
The reaction between quinoline-2-carboxylic acid (HQ) and lead(II) acetate trihydrate (Pb(OAc)2·3H2O) results in formation of kinetically stable and thermodynamically stable [Pb2(Q) 2(OAc)2]n (1) and [Pb(Q)2] n (2), respectively. Compound 1 (kinetically stable) was formed in aprotic solvent of acetonitrile and is stable in it. We evaluated the reaction between HQ and Pb(OAc)2·3H2O in two different ultrasonic baths and investigated the effect of initial reagents concentration on morphology and kind of resulting products. The resulting samples were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Although these reactions were performed in acetonitrile, only in two samples compound 1 was synthesized. Thus in other four samples, the resulting products were compound 2. Indeed, ultrasonic waves with ultra-high energy could change the kinetically stable 1 to thermodynamically stable 2 in acetonitrile. With the highest 0.1 M concentration of initial precursors, only thermodynamically stable product (2) obtained in both of two ultrasonic baths. In lower concentrations of initial precursors (0.025 M and 0.05 M), the kind of resulting product attributed to the type of ultrasonic bath and its wave power and frequency. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2014
Inorganica Chimica Acta (18733255) 416pp. 109-121
Three complexes with five-coordinate Cu(II), [Cu(tptz)Cl 2]·2H2O (1), [Cu(bpca)Cl]n (2) and [Cu(tptz)(dppz)](PF6)2 (3) (tptz = 2,4,6-tris(2-pyridyl)- 1,3,5-triazine, bpca = bis(2-pyridylcarbonyl)amidate anion, and dppz = dipyrido[3,2-a:2′,3′-c]phenazine) have been synthesized and characterized. Complex 2 was prepared from an aqueous solution of complex 1 via copper(II)-assisted hydrolysis of the tptz ligand. The solid state structures of complexes 1 and 2 have been determined by single-crystal X-ray crystallography. Complex 1 contains discrete neutral [Cu(tptz)Cl2] moieties, whereas complex 2 exhibits a polymeric chain arrangement built up of [Cu(bpca)Cl] units linked through the chloro ligands. In both complexes, the CuN3Cl 2 coordination polyhedra around the copper(II) centers are best described as nearly square-pyramidal, as ascertained by trigonality index τ value of 0.12 for 1 and 0.02 for 2. The interaction between complex 3 (as its nitrate salt) and calf thymus DNA (CT-DNA) has been investigated by electronic absorption, competitive fluorescence titration, circular dichroism, and flow linear dichroism. The results support the strong binding affinity of the complex to CT-DNA via an intercalative mode. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2014
Inorganica Chimica Acta (18733255) 414pp. 78-84
A series of salen type Schiff base ligands and their mononuclear (CuL n, n = 1-4) or dinuclear Cu(II) complexes (Cu2(L 5)2) were synthesized and characterized by 1H NMR, IR and UV-Vis spectroscopy as well as elemental analyses. The ligands were synthesized from the condensation of meso-1,2-diphenyl-1,2-ethylenediamine with various salicylaldehyde derivatives (x-salicylaldehyde for H2L n, x = H (n = 1), 5-Br (n = 2), 5-Br-3-NO2 (n = 3), 3-OMe, (n = 5)) and 2′-hydroxyacetophenone (n = 4). Crystal structures of two complexes (CuL4 and Cu2(L5)2) were determined. Catalytic performance of the complexes was studied in the epoxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant. Various factors including reaction temperature, solvent type, time, catalyst amount and substrate to oxidant ratio were optimized. High catalytic activity and epoxides selectivity was found. Solvent free epoxidation of cyclooctene was also studied and higher catalytic activity, epoxide selectivity and lower reaction times were observed. © 2014 Elsevier B.V. All rights reserved.
Darehkordi, A. ,
Rahmani, F. ,
Ramezani, M. ,
Askari, F. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2014
Journal Of The Iranian Chemical Society (1735207X) 11(6)pp. 1629-1638
o-Phenylenediamine derivatives and 2,3-diaminopyridine react with d-monosaccharides in ethanol-water in the presence of a catalytic amount of acetic acid along with p-toluidine under reflux condition to afford the corresponding quinoxalines or pyridopyrazin in high yields. These structures were confirmed by FT-IR, 1H-NMR, 13C-NMR, elemental analysis and single-crystal X-ray analysis. Graphical Abstract: [Figure not available: see fulltext.] © 2014 Iranian Chemical Society.
Landrani, A. ,
Mohammadpoor baltork, I. ,
Mirkhani, V. ,
Moghadam, M. ,
Khosropour, A.R. ,
Tangestaninejad, S. ,
Nasr-esfahani, M. ,
Amiri rudbari, H. Publication Date: 2014
Synlett (09365214) 25(5)pp. 645-652
A wide variety of diaryl sulfides has been synthesized in excellent yields via C-S cross-couplings of aryl/heteroaryl halides with aromatic/heteroaromatic thiols in the presence of palladium nanoparticles immobilized on nanosilica triazine dendritic polymer (Pd np -nSTDP) as a reusable catalyst under thermal conditions and microwave irradiation. Pd np -nSTDP also showed excellent catalytic activity for the preparation of a series of di- and trisulfides with benzene, pyridine, pyrimidine, and/or 1,3,5-triazine as the central cores by one-pot multi C-S cross-coupling reactions.© Georg Thieme Verlag Stuttgart. New York.
Mollaee, J. ,
Molaei, F. ,
Morsali, A. ,
Joo, S.W. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2014
Inorganic Chemistry Communications (13877003) 43pp. 67-69
A new two-dimensional silver(I) coordination polymer, [Ag(Quinoxaline) (NO3)]n (1); Quinoxaline = Benzopyrazine, has been synthesized and characterized by IR and 1H NMR spectroscopy. Silver nanorods were synthesized by calcination of compound 1 at 600 C under air atmosphere. Also, silver nanopowders and silver spongy nanostructures were synthesized by calcination at 400 and 500 C and sol-gel methods. The silver nanostructures were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and energy-dispersive X-ray (EDAX). The thermal stability of compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). © 2014 Elsevier B.V.
Publication Date: 2014
Journal of Sulfur Chemistry (17415993) 35(4)pp. 362-372
A series of novel ketene dithioacetals has been synthesized by condensation of active methylene compounds with carbon disulfide in the presence of dialkyl acetylenedicarboxylates. This regioselective reaction provides products in good yield by a Michael addition reaction followed by 5-endo-trig intramolecular cyclization. Structures of synthesized compounds have been characterized by elemental analysis, FT-IR, 1H NMR, 13C NMR, and mass spectra. The crystal structure of compound (C 17H 22O 6S 2) has been determined. © 2014 Taylor & Francis.
Publication Date: 2014
Journal of Molecular Structure (00222860) 1071(1)pp. 18-22
Two new coordination compounds [Fe(bib)2(N3) 2]n (1) and [Cu2(bpp)2(N 3)4] (2) with azide and flexible ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp) were prepared and structurally characterized. In the 2D network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while in the dinuclear structure of 2, the copper(II) ion adopts an FeN5 distorted square pyramid geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to copper(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2014
Polyhedron (02775387) 79pp. 306-314
Four new complexes, [Zn(tdmpp)2H2O](ClO 4)2·H2O (1), [Zn(NCS)Cl(tdmpp)] (2), [ZnI2(tdmpp)] (3) and [ZnCl2(tdmpp)] (4), were prepared and structurally characterized. The 1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazolyl) propane (tdmpp) ligand in the above compounds represents the first example of a flexible tetradentate nitrogen donor ligand in which the ligand is coordinated to the metal center as a terminal chelating ligand. The perchlorate ion in 1 acts as an uncoordinated anion, while in 2 the SCN and chlorine ligands and in 3 the iodine ligand participate in the coordination sphere of the metal center. The coordination ability of these anions and significant effects of non-covalent C-H⋯π and C-H⋯X (X = O, Cl and I) interactions play a major role in the crystal packing of these compounds. In 1, the zinc atom adopts a distorted trigonal bipyramidal geometry and the [Zn(tdmpp)2H 2O]2+ cations are linked by C-H⋯O hydrogen bonds to give a 1-D chain structure. In the structures of 2 and 3, the mononuclear neutral molecules form a 1-D chain structure along the b-axis through C-H⋯Cl and C-H⋯I hydrogen bonds, respectively. These chains are linked by intermolecular C-H⋯π interactions to generate a three-dimensional network. Crystals of compound 4 were not suitable for X-ray diffraction studies and therefore its structure could only be investigated in the solid state by infrared spectroscopy and elemental analysis. © 2014 Elsevier Ltd. All rights reserved.
Keypour, H. ,
Zebarjadian, M.H. ,
Rezaeivala, M. ,
Chehreghani, A. ,
Amiri rudbari, H. ,
Bruno, G. Publication Date: 2014
Journal Of The Iranian Chemical Society (1735207X) 11(1)pp. 101-109
Two new branched hexadentate amines, 4,8-bis(2-pyridylmethyl)-4,8- diazaundecane-1,11-diamine (1) and 4,9-bis(2-pyridylmethyl)-4,9-diazadodecane-1, 12-diamine (2), have been synthesized. Condensation with 2,6-diacetylpyridine in methanol in the presence of manganese(II), zinc(II) and cadmium(II) ions leads to produce some new Schiff base macrocyclic complexes with two 2-pyridylmethyl pendant arms. The X-ray crystal structure of the resulting manganese(II) complex, [MnL1](ClO4)2 ·H2O (3), is reported here. It has been shown that the manganese atom is bonded to five nitrogens of a macrocyclic ring and two nitrogens of the pendant arms. The arrangement is slightly distorted to pentagonal bipyramidal whereas the nitrogens of 2-pyridylmethyl groups occupy apical positions. The synthesized complexes were screened for their antibacterial activities against four bacterial strains and the complexes showed antibacterial effects. Graphical Abstract: [Figure not available: see fulltext.] © 2013 Iranian Chemical Society.
Grivani, G. ,
Vakili, M. ,
Khalaji, A.D. ,
Bruno, G. ,
Amiri rudbari, H. ,
Taghavi, M. ,
Tahmasebi, V. Publication Date: 2014
Journal of Molecular Structure (00222860) 1072(1)pp. 77-83
The Nickel (II) Schiff base complex of NiL2, (L = 2-{(E)-[2-chloroethyl) imino]methylphenolate) have been synthesized and characterized by elemental (CHN) analysis, UV-vis and FT-IR spectroscopy. The molecular structure of [NiL2] was determined by single crystal X-ray diffraction technique. The Schiff base ligand HL acts as a chelating ligand and coordinates via one nitrogen atom and one oxygen atom to the metal center. The nickel (II) center is coordinated by two nitrogen and two oxygen atoms from two Schiff base ligands in an approximately square planar trans-[MN 2O2] coordination geometry. Thermogravimetric analysis of NiL2 showed that it decomposed in three stages. In addition, complex NiL2 thermally decomposed in air at 660 °C and the XRD pattern of the obtained solid showed the formation of NiO nanoparticles with an average size of 43 nm. In addition, the conformational analysis and molecular structures of NiL2 were investigated by means of density functional theory (DFT) calculations at B3LYP/6-311G* level and the calculated geometrical parameters were compared with the experimental results. © 2014 Elsevier B.V. All rights reserved.
Publication Date: 2014
Comptes Rendus Chimie (18781543) 17(11)pp. 1144-1153
In this study, the syntheses of two new Mo(VI) and Ni(II) complexes with H2L tridentate (ONO) Schiff-base ligand have been described and fully characterized by means of elemental analysis, FT-IR, electronic, 1H-NMR spectroscopy and single-crystal X-ray diffraction. In both complexes, the Schiff-base completely deprotonates and coordinates to the metal ion as a dianionic tridentate ligand via the donor oxygens and nitrogen atoms. The coordination numbers of Mo(VI) and Ni(II) are six and four, respectively. The DFTB3LYP/6-31 + G (d,p) and PBEPBE/6-31 + G (d,p) calculations are carried out for the determination of the optimized structures. Frequency calculations and NBO analysis are also performed for characterization. According to the theoretical analysis of the complexes, ligand-to-metal donation is greater than back donation. NBO data revealed that the main contribution of the frontier orbitals belongs to L-2. © 2014 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Derikvand, Z. ,
Bruno, G. ,
Amiri rudbari, H. ,
Shokrollahi, A. ,
Zarghampour, F. ,
Azadbakht, A. Publication Date: 2014
Inorganica Chimica Acta (18733255) 410pp. 221-229
Two new 2D heteronuclear coordination polymers with Ni(II), Zn(II) and Ca(II), namely {(dapH)2[CaM2(pydc)4(H 2O)2]·2H2O}n (M = Ni (1) and M = Zn (2)) where [pydcH2 = pyridine-2,6-dicarboxylic acid (dipicolinic acid), dap = 3,4-diaminopyridine] have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermal (TG/DTG/DTA) analysis, electrochemical as well as X-ray single crystal diffraction. The compounds 1 and 2 display isostructural features and crystallized in the monoclinic P21/n space group. Both of the compounds contain cationic and anionic fragments and two uncoordinated water molecules. In 1 and 2 (pydc)2- acts as tridentate ligands and connected to calcium ions through carboxylate bridging. Then each dipicolinate ligand bridges one calcium to a M(II) atom. The equilibrium constants of the binary, ternary and quaternary complexes of ligands or proton transfer system with metal ions in an aqueous solution were investigated by a potentiometric pH titration method. © 2013 Elsevier B.V. All rights reserved.
Sedaghat, T. ,
Yousefi, M. ,
Bruno, G. ,
Amiri rudbari, H. ,
Motamedi, H. ,
Nobakht, V. Publication Date: 2014
Polyhedron (02775387) 79pp. 88-96
The new diorganotin(IV) complexes R2SnL (L = La: R = Me 1, Ph 2; L = Lb: R = Me 3, Ph 4, L = Lc: R = Me 5, Ph 6, Bu 7) have been synthesized by the reaction of the hydrazone ligands N′-(5-bromo-2-hydroxybenzylidene) isonicotinohydrazide (H 2La), N′-((2-hydroxynaphthalen-1-yl)methylene) isonicotinohydrazide (H2Lb) and N′-(2,4- dihydroxybenzylidene) isonicotinohydrazide (H2Lc) with diorganotin(IV) dichloride. The synthesised compounds have been investigated by elemental analysis, together with IR, 1H and 119Sn NMR spectroscopy. The structures of H2La, H2L b and 3 have also been confirmed by X-ray crystallography. On the basis of these data, H2La and H2Lb are present in the keto-amine tautomeric form and intermolecular N-H⋯N hydrogen bonds form 1D chain structures. The hydrazone ligands act as tridentate dibasic in the enol form and are coordinated via the imine nitrogen, phenolate and enolate oxygen atoms. The in vitro antibacterial activity of the ligands and their complexes has been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria and compared with standard antibacterial drugs. The R 2SnLc complexes exhibited greater activities than the other compounds. © 2014 Elsevier Ltd. All rights reserved.
Publication Date: 2014
Polyhedron (02775387) 68pp. 372-378
Treatments of the flexible 1,4-bis(imidazolyl)butane (bib) ligand with Fe(II) salts in a mixture of ethanol and water (1:1) as a solvent at room temperature resulted in the formation of two novel coordination polymers, {[Fe(bib)3](ClO4)2}n (1) and {[Fe(bib)3](PF6)2}n (2), with two distinctly different network structures due to the variation of the ClO 4- and PF6- moieties in these compounds. Their infrared spectra, X-ray powder diffraction (XRPD), elemental and thermal analyses were also investigated in detail. The results of the X-ray analyses demonstrate that in these structures, the iron(II) ion lies on an inversion center and adopts an FeN6 octahedral geometry. Each μ2-bib serves as a bridging ligand connecting two adjacent iron(II) ions. In the structure of 1, six μ2-bib ligands are simultaneously coordinated to one central iron(II) ion to form an open 3D 2-fold interpenetrating framework with an α-polonium (pcu) topology, while 2 has an open 3D network with an acs [point symbol (49.66)] structure. The structure of [bibMeH](PF6) [bib Me = 1,4-bis(2-methylimidazolyl)butane] (3) has also been studied by X-ray crystallography as an unexpected product in an attempt to synthesize the {[Fe(bibMe)3]2+}n cation with the PF6- anion. © 2013 Published by Elsevier Ltd.
Publication Date: 2014
Inorganica Chimica Acta (18733255) 409(PART B)pp. 379-389
The mononuclear Co(II) complex, trans-[Co(Pir)2(DMF) 2], where Pir is piroxicam, has been prepared in two different ionic liquids and fully characterized. The interaction of the complex with CT-DNA and BSA has been monitored using different analytical methods. The results have indicated that the complex binds to CT-DNA by a groove mode and also a partial insertion of a Pir ligand between the base stacks of DNA. The molecular docking of the complex with DNA has revealed that the complex can fit into the major groove and is stabilized by intermolecular hydrogen bonding and hydrophobic interactions. The results have also shown a moderate binding propensity of the complex to BSA. The molecular modeling has indicated that the binding mode of the complex to BSA is of hydrophobic and hydrogen bond interactions. © 2013 Elsevier B.V. All rights reserved.
Publication Date: 2013
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy (13861425) 110pp. 124-129
A new Cu(II) complex [Cu(L)(NCS)] has been synthesized, using 1-(N-salicylideneimino)-2-(N,N-methyl)-aminoethane as tridentate ONN donor Schiff base ligand (HL). The dark green crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FT-IR) and UV-Visible spectra. Electronic structure calculations at the B3LYP and MP2 levels of theory are performed to optimize the molecular geometry and to calculate the UV-Visible and FT-IR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TD-DFT) method is used to calculate the electronic transitions of the complex. A scaling factor of 1.015 is obtained for vibrational frequencies computed at the B3LYP level using basis sets 6-311G(d,p). It is found that solvent has a profound effect on the electronic absorption spectrum. The UV-Visible spectrum of the complex recorded in DMSO and DMF solution can be correctly predicted by a model in which DMSO and DMF molecules are coordinated to the central Cu atom via their oxygen atoms. © 2013 Elsevier B.V. All rights reserved.
Publication Date: 2013
Journal of Organometallic Chemistry (0022328X) 737pp. 26-31
New organotin(IV) complexes, (R2Sn)2L [L = L a: R = Me (1), Ph (2); L = Lb: R = Me (3), Ph (4)] have been synthesized by reaction of dihydrazone ligands, bis(5-bromosalicylaldehyde) adipicdihydrazone (H4La) and bis(2-hydroxynaphthaldehyde) adipicdihydrazone (H4Lb) with R2SnCl 2 (R = Me or Ph). The synthesized compounds have been investigated by elemental analysis and IR, 1H NMR, and 119Sn NMR spectroscopy. The structures of 1 and 4 have been also confirmed by X-ray crystallography. The results show that the dihydrazone acts as a tetrabasic ligand in the enolic form and is coordinated to two diorganotin moiety via the imine nitrogen and phenolic and enolic oxygen atoms. All complexes are binuclear and the coordination number of each tin is five. The in vitro antibacterial activity of ligands and complexes has been evaluated against Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria and compared with standard drugs. All complexes exhibit more inhibitory effects than the parent ligands. © 2013 Elsevier B.V. All rights reserved.
Haghighi, F.H. ,
Hadadzadeh h., H. ,
Darabi, F. ,
Farrokhpour h., H. ,
Daryanavard, M. ,
Amiri rudbari, H. Publication Date: 2013
Journal of Molecular Structure (00222860) 1040pp. 98-111
In this paper, a mononuclear tris(chelate) ruthenium(II) complex, [Ru(phen-diox)3](PF6)2 (1) and its diaqua derivative, [Ru(phen-diox)2(H2O)2](PF 6)2 (2), where phen-diox is 2,3-dihydro-4a,12b- (epoxyethanooxy)[1,4]dioxino[2,3-f][1,10]phenanthroline, have been prepared based on the condensation reaction of the coordinated 1,10-phenanthroline-5,6- dione (phen-dione) ligand with ethylene glycol using the metal-assisted effect. The condensation reaction could not occur in the absence of [Ru(phen-dione) 3]2+ or [Ru(phen-dione)2(H2O) 2]2+ complex. The computational studies have demonstrated that the energy of the LUMO of [Ru(phen-dione)3]2+ is about 129 kcal/mol lower than the uncoordinated phen-dione molecule. The complexes have been characterized by elemental analysis and spectroscopic techniques. The X-ray analysis of [Ru(phen-diox)3](PF 6)2 (1) shows a distorted octahedral RuN6 coordination geometry around the ruthenium atom. The interaction of the complexes with DNA has been monitored by UV-Vis, fluorescence and voltammetric (CV and DPV) techniques. The Kb values of (1) and (2) for DNA binding were determined 1 × 103 and 2 × 103 M -1, respectively. Furthermore, other experiments reveal that the binding affinity of (2) is stronger than (1). The results show that the complexes interact with DNA through the groove and hydrogen bonding of the acetal oxygens of the phen-diox ligands with the nucleobases of DNA. Also, complex (2) possibly interacts with DNA via covalent bonding. © 2013 Elsevier B.V. All rights reserved.
Iranmanesh, H. ,
Behzad, M. ,
Bruno, G. ,
Amiri rudbari, H. ,
Nazari, H. ,
Mohammadi, A. ,
Taheri, O. Publication Date: 2013
Inorganica Chimica Acta (18733255) 395pp. 81-88
Four new N2O2 type tetradentate Schiff base complexes of Co(III), [Co(Lx)(py)2]PF6 (CoLx, x = 1,3-4), and [CoNa(L2)(py)(OAc)(CH3CH(OH)CH 3)(H2O)]ClO4·(CH3CH(OH) CH3), (CoNaL2), where Lxs are tetradentate Schiff base ligands derived from the condensation of meso-1,2-diphenyl-1,2- ethylenediamine (mesostilbenediamine) with salicylaldehyde derivatives, were synthesized and characterized by elemental analysis, 1H NMR, IR, and UV-Vis spectroscopy. X-ray crystal structures of CoNaL2 and CoL 3were also determined. In CoNaL2, sodium atom is coordinated to CoL2 moiety via two oxygen atoms of 3-OMe groups of salicylaldehyde part. A bridging acetate ion also has bridged the Co and Na centers. Cyclic voltammetry studies revealed that all of the complexes showed a one-electron reversible oxidation wave related to CoIII/IV couple in the anodic region. Two reduction waves for CoIII/II and Co II/I couples were also observed. The in vitro antimicrobial activity of the Schiff base complexes was tested against human pathogenic bacteria such as Salmonella typhi, Pseudomonas aeruginosa, Klebsiella pneumonia, Staphylococcus aureus and Listeria monocytogenes. All of the complexes showed moderate antibacterial activities against both Gram positive and Gram negative bacteria. © 2012 Elsevier B.V. All rights reserved.
Publication Date: 2013
Journal of Coordination Chemistry (10290389) 66(2)pp. 345-357
A new tridentate Schiff base, 5-bromosalicylaldehyde S- allylisothiosemicarbazone hydrobromide (H2L), and several new mononuclear complexes of copper(II) and molybdenum(VI) of this ligand with general formulas ([Cu(L)Im] (1)), ([Cu(L)NH3].4H2O (2)), and ([MoO2(L)1-MeIm] (3), Imidazole: Im, 1-methylimidazole: 1-MeIm) were prepared and characterized by elemental analyses, IR, Proton Magnetic Resonance Spectroscopy and Ultraviolet-visible techniques. The physico-chemical results suggested that the H2L coordinates in the dianionic tridentate form. Crystal structures of the Cu(II) complexes reveal a square planar configuration surrounded by the dianionic tridentate isothiosemicarbazone (ONN) and Im and NH3 for 1 and 2, respectively. The L2-, two oxo, and 1-methylimidazole are coordinated to molybdenum(VI) in a distorted octahedral geometry in 3. Formation of pure metal oxide residues was confirmed by thermal degradation of the complexes. © 2012 Taylor and Francis.
Publication Date: 2013
Crystallography Reports (10637745) 58(7)pp. 1084-1087
The crystal structure of 1-Methyl-3-([2,2-dimethyl-4,6-dioxo-1,3-dioxane-5- ylidene]methyl)urea (C9H12N2O5) has been determined by single crystal X-ray diffraction analysis. The crystals are monoclinic, a = 5.3179(2), b = 18.6394(6), c =10.8124(3) Å, β = 100.015(2), Z = 4, sp. gr. P21/c, R = 0.0381 for 2537 reflections with I > 2σ(I). Except for C(CH3)2 group, the molecule is planar. The structure is stabilized by inter- and intramolecular N-H.O hydrogen bonds and weak C-H.O interactions. © 2013 Pleiades Publishing, Inc.
Saghatforoush, L. ,
Amiri rudbari, H. ,
Nicolò, F. ,
Asgari, P. ,
Chalabian, F. ,
Katozian, F. Publication Date: 2013
Main Group Chemistry (17451167) 12(4)pp. 349-360
The new 1D coordination polymer, [Cd(Clphtpy)(NCS)(NO3)] n (Clphtpy = 4'- chlorophenyl-2,2':6',2''-terpyridine), was prepared and characterized by CHN elemental analysis, 1H NMR-, IR spectroscopy and analyzed structurally by X-ray single-crystal diffraction. X-ray crystallography data showed that the asymmetric unit of complex comprised an independent mononuclear cadmium complex with a seven-coordinate "CdN 4O2S" core. The complex was tested against four gram-positive and four gram-negative bacteria. It exhibited good activity against most of the bacteria and its activity was better than gentamicin as a standard antibiotic. The luminescence properties of the free ligand and the complex were investigated.© 2013 - IOS Press and the authors. All rights reserved.
Publication Date: 2013
Journal of Coordination Chemistry (10290389) 66(13)pp. 2250-2263
Two new mixed-chelate dinuclear copper(II) complexes, [Cu2(tmen)2(TAP)]X2 where tmen = N,N,N',N'- tetramethylethylenediamine, TAP= tetraacetylpropane, and X=ClO4 or BPh4 , were prepared and characterized by physicochemical and spectral (IR, UV-vis) data. The X-ray diffraction study of [{Cu(tmen) (CH3CN)}{Cu(tmen)(ClO4)}(TAP)](ClO4) demonstrated that coordination geometry around the copper centers is square pyramidal where axial position of one copper is occupied by a ClO4 and the second copper with acetonitrile. However, in solution, the resulting complexes display affinity for axial ligation so that the apical ligands are driven out by solvent molecules. The solvatochromism of the complexes was investigated in various organic solvents and was compared with that of the corresponding mononuclear complex [Cu(tmen)(CH3-acac)]ClO4. A multi-parametric equation has been utilized to explain the solvent effect on the d-d transition of the complexes using SPSS/PC software. To explore the mechanism of the interaction between the solvent molecules and the complexes, different solvent parameters such as DN, AN, a, ET(30), p/, and β using stepwise multiple linear regression method were employed. In pyridine, the original color of the solution changed over time due to removal of tmen chelates and substitution by pyridine in two successive steps. © 2013 Taylor and Francis.
Publication Date: 2013
Journal Of The Iranian Chemical Society (1735207X) 10(1)pp. 29-41
A series of mono- and heterodinuclear macro-acyclic complexes of [ZnLCu(II)]2+ and [ZnLNi(II)]2+ were synthesized by a stepwise procedure. The phenol-based macro-acyclic dicompartmental ligands (L2-) possess contagious hexadentate (N4O2) and tetradentate (N2O2) coordination sites, where in the mononuclear complexes [ZnL(H+)2]2+ the latter site containing two alkyl-imine donor groups (ethyl or isopropyl) is attached to the azomethine moieties. The alkyl group(s) is eliminated upon introduction of the second metal (II) ion into N2O2 coordination site as a result of steric crowding of the alkyl groups along with the lack of flexibility associated with the imine groups. When the second metal ion is Cu(II) and R = isopropyl, the both of them are eliminated but when R = Et only one ethyl group is removed. However, in case of Ni(II) as the second metal ion, the both alkyl groups are eliminated regardless of the nature of the alkyl group. The origins of the structural variations are discussed. The prepared complexes were characterized by elemental analysis, molar conductance measurements, X-ray crystallography, IR, NMR and UV-Vis spectroscopies. © 2012 Iranian Chemical Society.
Publication Date: 2013
European Journal of Medicinal Chemistry (02235234) 69pp. 577-590
A mononuclear Ru(II) complex containing two piroxicam (Pir-) ligands was synthesized and fully characterized. Interaction studies of the Pir- anion and the Ru(II) complex with DNA and BSA were carried out using spectroscopic techniques. The results suggested that the Pir- anion binds to DNA in a moderately strong fashion via intercalation between the base stacks of double-stranded DNA, while the Ru(II) complex is a groove binder and interacts with DNA with more affinity. Moreover, the results demonstrated that the microenvironment and the secondary structure of BSA were changed in the presence of Pir†and Ru(II) complex. The free Pir †ligand and the Ru(II) complex can lead to the photocleavage of DNA supercoiled pUC57. Finally, the binding of the Ru(II) complex to BSA and DNA was modeled by molecular docking and molecular dynamic simulation methods. © 2013 Elsevier Masson SAS. All rights reserved.
Publication Date: 2013
Journal of Molecular Structure (00222860) 1051pp. 244-249
Iron(II) coordination compounds [Fe(bib)2(NCS)2] n (1) and [Fe(bpp)(NCS)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), mono-anionic NCS- ligand and appropriate iron(II) salts. In the CdSO4 network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN 6 octahedral arrangement while, in the monomeric structure of 2, the iron(II) ion adopts an FeN4 tetrahedral geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to an iron(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied. An attempt to synthesize [Fe(bbd)(NCS)2] (3) (bbd = 1,4-bis(3,5-dimethylpyrazolyl)butane) with the reaction of bbd, Fe(NH4)2(SO4) 2·6H2O and KNCS was failed. © 2013 Published by Elsevier B.V.
Publication Date: 2013
Central European Journal of Chemistry (18951066) 11(11)pp. 1844-1851
A new Schiff base ligand of 5-bromo-2-hydroxybenzaldehyde S-ethyl-isothiosemicarbazone (H2L) was synthesized and its mixed-ligand Cu(II) complex was also prepared by reaction of Cu(NO 3)2·3H2O with H2L and imidazole. Their structures were fully characterized by elemental analysis, FT-IR, molar conductivity and UV-Vis methods. The analytical data suggest that the metal, H2L and imidazole ratios in the Schiff base complex are 1:1:1. Single crystal diffraction was also used to better understand the molecular structure of the Cu(II) complex. The results of physico-chemical analyses of the Schiff base complex reveal the coordination geometry around the central atom is square planar. The H2L ligand (NNO donor) is coordinated to the metal center as a tridentate bionegatively agent. Another position of the square planar geometry is occupied by the imidazole ligand. Furthermore, computational studies of the new complex were performed by carrying out DFT calculations. Geometry optimization and natural band analysis of the complex is discussed in further detail. [Figure not available: see fulltext.] © 2013 Versita Warsaw and Springer-Verlag Wien.
Haghighi, F.H. ,
Hadadzadeh h., H. ,
Darabi, F. ,
Jannesari, Z. ,
Ebrahimi, M. ,
Khayamian, T. ,
Salimi, M. ,
Amiri rudbari, H. Publication Date: 2013
Polyhedron (02775387) 65pp. 16-30
The mononuclear Ni(II) complex, [Ni(tppz)2]2+, where tppz is 2,3,5,6-tetra(2-pyridyl)pyrazine, has been prepared and characterized by elemental analysis, spectroscopic methods and single crystal X-ray structure analysis. The interaction of the complex with calf-thymus DNA (CT-DNA) has been monitored by UV-Vis, competitive fluorescence titration, circular dichroism (CD), voltammetric techniques and gel electrophoresis. The results have indicated that the complex binds to CT-DNA by three biding modes, viz., electrostatic, groove and partial insertion of a pyridyl ring of the tppz ligand between the base stacks of double-stranded DNA. The molecular docking of the complex with DNA sequence d(ACCGACGTCGGT)2 suggests two binding modes, viz., groove and partial intercalative binding. The results have also shown good binding propensity of the complex to BSA. The molecular modeling has indicated that the binding mode of the complex to BSA is of hydrophobic forces and hydrogen bond interaction. © 2013 Elsevier Ltd. All rights reserved.
Publication Date: 2013
Journal of Coordination Chemistry (10290389) 66(8)pp. 1374-1383
Six new complexes were synthesized in a 0.1M aqueous carbonate solution and characterized by elemental analyses, thermogravimetric analyses, infrared spectroscopy and X-ray single crystal structure analyses. The single-crystal structure analysis was on K11[(A-AsW9O34)2(H 2ODy)3-CO3]22H2O. The results revealed that the complexes are isomorphic and their structures consist of two lacunary [A-XW9O34]9- Keggin moieties linked by a (OMOH2)3C belt, forming an A-type sandwich structure. The CO2 3 is tridentate and fixes three M3+ centers together by its oxygens. Each M3+ cation is mono-capped trigonal-prismatic coordination, achieved by two terminal oxygens of an edge-shared pair of WO 6 octahedra to each [A-XW9O34]9- and two oxygens from the belt, and the cap by one water. © 2013 Taylor & Francis.
Publication Date: 2013
Inorganica Chimica Acta (18733255) 408pp. 214-221
Iron(II) coordination polymers {[Fe(bix)2(NCS) 2]·H2O}n (1) and [Fe(bix) 2(N3)2]n (2) were synthesized using the flexible bidentate N-donor 1,4-bis(imidazol-1-ylmethyl)benzene (bix) ligand together with the mono-anionic ligands such as NCS- and N 3- ions. In both of these complexes the iron(II) ion is in a distorted octahedral arrangement. Polymers 1 and 2, exhibit 2D framework with the ABCDE. and ABAB. packing modes, respectively. By considering the non-classical C-H⋯N hydrogen bonds, complex 2 is a three-dimensional polymer. Due to the presence of seven different kinds of trans-gauche conformations of the flexible bix ligands in the asymmetric unit of 1, there are four crystallographically independent iron(II) ions. In contrast to 1, in complex 2, all the bix ligands have the same conformation (trans-gauche). So, there is only one kind of iron(II) ion in this structure. Moreover, an attempted synthesis of [Fe(bix)3](ClO4)2 lead to the formation of unexpected diprotonated ionic species [bixH2](ClO 4)2 (3) which was identified by X-ray analysis and infrared spectroscopy. Polymers 1 and 2 have been characterized by infrared spectroscopy, elemental and thermal analyses and single-crystal X-ray diffraction. © 2013 Elsevier B.V. All rights reserved.
Publication Date: 2013
Inorganica Chimica Acta (18733255) 394pp. 1-9
Three new mixed-chelate Cu(II) complexes incorporating N,N,N′, N′-tetramethylenediamine (tmen) or N,N-dimethyl,N′-benzyl- ethylenediamine (dmben) as diamine chelate and a β-ketoaminato such as 4-amino-3-penten-2-onato (APO) or 3-amino-3-phenyl-2-buten-1-onato (APBO) with the general formula [Cu(β-ketoamine)(diamine)]ClO4 were prepared and characterized. Their solvatochromic properties were studied by visible spectroscopy. X-ray crystal analysis confirmed that copper (II) ion in [Cu(APO)(tmen)]ClO4 and[Cu(APBO)(tmen)]ClO4 is almost in a square planar environment. Structure of [Cu(APO)(dmben)]ClO4 was investigated by DFT calculation. The solvent-dependent visible spectroscopic absorption maxima, νmax, were analyzed using stepwise multiple linear regression (SMLR) method to find the best model explaining the observed positive solvatochromism. The analysis demonstrated that among different solvent parameters, donor number (DN) is a dominant factor responsible for the shift in the d-d absorption band of the complexes to the lower wavenumber with increasing its values. The importance of steric effect in the diamine ligand and more delocalization of pi-bands in the β-ketoamine on the spectral and SMLR measurements are discussed. © 2012 Elsevier B.V. All rights reserved.
Azadbakht, R. ,
Khodabandeh, M. ,
Keypour, H. ,
Baghdad abadi, R.H.H. ,
Amiri rudbari, H. Publication Date: 2013
Journal of Heterocyclic Chemistry (0022152X) 50(4)pp. 979-981
Three tetra-amine compounds 2-((2-(2-aminobenzylamino)ethylamino)methyl) benzenamine (L1), 2-((3-(2-aminobenzylamino)propylamino)methyl) benzenamine (L2), and 2-((4-(2-aminobenzylamino)butylamino)methyl) benzenamine (L3) were synthesized and then their reaction with 2-hydroxybenzaldehyde, 2-nitrobenzaldehyde, and 2-hydroxy-3-methoxybenzaldehyde were investigated. Treatment of L1, L2, and L3 with the former aldehydes gave derivatives of quinazolines in a good yield. The products have been studied with IR, 1H NMR, 13C NMR, COSY, HMQC, and microanalysis. © 2013 HeteroCorporation.
Publication Date: 2013
Journal of Molecular Structure (00222860) 1036pp. 71-77
Three new cadmium(II) complexes, [Cd2(TPT)2(SCN) 4]·H2O (1), [Cd(TPT)I2] (2) and [Cd(TPT)Br2] (3) ("TPT" is the abbreviation of 3,5,6-tris(2-pyridyl)-1,2,4-triazine), have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, and studied by thermal gravimetric as well as X-ray single crystal diffraction. Two anions of four thiocyanate anions bridge two CdII ions to form a dinuclear complex, 1, and iodide and bromide ions produce two halide-coordinated [Cd(TPT)X2] complexes (X = I for 2 and Br for 3). Cadmium(II) in 1 is six coordinate, CdN4S2 and in 2 and 3 is five coordinate, CdN3I2 and CdN3Br2. The supramolecular features in these complexes are guided/controlled by N⋯O hydrogen bonding (in 1) and weak directional intermolecular CH⋯N, Cg⋯I, CH⋯Br and π-π interactions. © 2012 Elsevier B.V. All rights reserved.
Mohammadi, M. ,
Akhbari, K. ,
Hanifehpour, Y. ,
Morsali, A. ,
Joo, S.W. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2013
Journal of Organometallic Chemistry (0022328X) 733pp. 15-20
A new thallium(I) two-dimensional supramolecular polymer, [Tl 6(biphO)4(biphOH)4(NO3) 2]n (1), biphOH = 4-hydroxy biphenyl, has been synthesized and characterized by elemental analyzes and IR spectroscopy. Compound 1 was structurally characterized by single-crystal X-ray diffraction and in addition to three types of TlI ions has secondary Tl⋯π Interactions. Two different Tl2O3 nano-structures have been prepared by direct calcination of 1 at two different temperatures. These Tl 2O3 nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction (XRD) and IR spectroscopy. This study demonstrates the coordination polymers may be suitable precursors for the preparation of nanoscale materials with various and interesting morphologies; however the final morphology of Tl2O3 can be influenced by calcination temperature. © 2013 Elsevier B.V. All rights reserved.
Grivani, G. ,
Tahmasebi, V. ,
Eskandari, K. ,
Khalaji, A.D. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2013
Journal of Molecular Structure (00222860) 1054pp. 100-106
Two new Schiff base compounds 2-{(E)-[2-(bromoethyl)iminolmethyl)-4-bromophenol (1) and 2-{(E)-[2-(chloroethyl)iminolmethyl)-4-bromophenol (2) have been synthesized and characterized by FT-IR and H-1 NMR spectroscopy, elemental analysis, thermal studies and single-crystal X-ray diffraction. They crystallize in the triclinic system, space group P-1. Both Schiff base compounds 1 and 2 display a trans configuration with respect to the C=N double bond. Quantum theory of atoms in molecules (QTAIM) has been also used to find intramolecular interactions and investigate their chemical nature. The results show that in both of the compounds 1 and 2, there is a hydrogen bonding between nitrogen of imine and oxygen of phenol which is considerably stronger than normal hydrogen bonds. In addition, it has been shown that these hydrogen bonds are partially covalent and partially electrostatic in nature, in contrast to normal hydrogen bonds, which are usually considered as electrostatic interactions. (C) 2013 Elsevier B.V. All rights reserved.
Saghatforoush, L. ,
Amiri rudbari, H. ,
Nicolò, F. ,
Asgari, P. ,
Chalabian, F. ,
Hasanzadeh, M. ,
Panahiazar, V. Publication Date: 2013
Acta Chimica Slovenica (15803155) 60(2)pp. 300-309
Two new Cd(II) complexes, with the ligand 4'-(4-chlorophenyl)-2,2':6',2''- terpyridine (Clphtpy) formulated as: [Cd(Clphtpy)(NO3) 2H2O] (1), and [Cd(Clphtpy)(N3) 2]2 (2), have been synthesized and characterized by CHN elemental analysis as well as FT-IR, 1H NMR, absorption and emission spectroscopy, thermal analysis and analyzed structurally by X-ray single-crystal diffraction. The single crystal X-ray analysis showed that the coordination number in complex 1 and 2 were seven and six with N3O4 and N6 coordination sphere, respectively. The antibacterial activities of the synthesized complexes were tested against four gram-positive and four gram-negative bacteria. A biological study of the complexes indicated that the complex 1 exhibited very good activity against most of the tested bacteria and its activity was better than gentamicin as a standard antibiotic.
Publication Date: 2013
Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya (10703284) 39(12)pp. 867-871
The synthesis, spectroscopic, and magnetic characterization of two new copper(II) and cobalt(II) complexes are described. Both two compounds have the general formula [M(L)2(Cl)2] (M = Cu (I), Co (II); L = 2-amino-5-bromopyridine). These complexes were prepared in one-step synthesis and characterized by elemental analysis, FT-IR, UV-Vis, and EPR spectroscopy. Moreover, the single crystal structure of com- plex I was studied by the X-ray diffraction method. This compound consists of mononuclear units consisting of two ligands linked to metal via the nitrogen of pyridine ring. The UV-Vis spectra of copper(II) and cobalt(II) complexes show three and five absorption bands, respectively, attributed to the d-d transition of the metal ion, ligand → metal charge transfer and π → π* or n → π* transitions of the ligand. The FT-IR spectra show MN2Cl2 vibrations at 500-300 cm-1. The complexes show room temperature magnetic moments of 1.78 and 4.12 μB for Cu(II) and Co(II), respectively. The X-band electron spin resonance (ESR) spectra of Cu(II) complex in DMF or DMSO frozen at liquid nitrogen temperature show the typical ΔMS = ±1 transition. © Pleiades Publishing, Ltd., 2013.
Publication Date: 2013
Polyhedron (02775387) 55pp. 225-232
Four new compounds, 3-methoxy-2-hydroxybenzaldehyde S- ethylisothiosemicarbazone (H2L), (3-methoxy-2-hydroxybenzaldehyde S-ethyl-isothiosemicarbazonato-N,N′,O)-(1-methylimidazole)-nickel(II) (1), (3-methoxy-2-hydroxybenzaldehyde S-ethyl-isothiosemicarbazonato-N,N′,O)- (pyridine)-nickel(II) (2) and cis-dioxo-dimethylsulfoxide-(3-methoxy-2- hydroxybenzaldehyde S-ethyl-isothiosemicarbazonato-N,N′,O)-molybdenum(VI) (3), have been synthesized and characterized by molar conductivity, FT-IR, UV-Vis, 1H NMR, elemental analysis and X-ray crystal structures. The crystal structure of H2L reveals that the NH2 and S-R moieties are in cis positions with respect to each other, and the molecule adopts the Z configuration. The ligand is bonded to the central metals as a binegatively tridentate agent. The Ni(II) atom adopts square planar geometry with this ligand, with the 1-methylimidazole and pyridine ligands occupying the remaining position in complexes 1 and 2 respectively. The Mo(VI) center in complex 3 is six coordinated by the ligand, two oxido groups and one DMSO molecule. The Density Functional Theory approach has been successfully used for the investigation of the ground state, frequency assignment and natural bond analysis. © 2013 Elsevier Ltd. All rights reserved.
Karami, K. ,
Salimian, M. ,
Hosseini-kharat, M. ,
Bruno, G. ,
Amiri rudbari, H. ,
Tavakol, H. Publication Date: 2013
Polyhedron (02775387) 61pp. 143-150
The phosphorus ylide [Ph3PCHC(O)C6H 4-NO2-4] (1) reacted with Pd(OAc)2 to give the C, C-orthometallated complexes [Pd{K2(C, C)-C6H 4PPh2C(H)CO(C6H4-NO2-4)}(μ-X)] 2 (X = Cl (2); X = Br (3)) as a mixture of isomers, which underwent bridge cleavage reactions with monodentate ligands to afford the monomeric, neutral Pd(II) complexes [Pd{κ2(C, C)-C6H 4PPh2C(H)CO(C6H4-NO 2-4)}X(L)] (X = Cl, L=Me3Py (4), PPh3 (5); X = Br, L = Me3Py (6), 4-MePy (7), PPh3 (8). The complexes were identified and characterized by spectroscopic studies (IR and NMR). The X-ray single crystal analysis of 6 and 7 revealed the presence of an orthometallated C6H4-2-PPh2 unit and a C-linked ylide, Pd-C(H). In the crystal structure of 6, the location of the Me3Py ligand is trans to the Pd-Cylide, according to the anti-symbiotic effect, whereas in 7 the 4-MePy ligand is preferentially cis to the Pd-Cylide. Density functional theory (DFT) calculations in the reaction solvent (dichloromethane) indicated that the trans isomers of 6 and 7 are 3.03 and 0.70 kcal/mol more stable than their cis isomers, respectively. © 2013 Elsevier Ltd. All rights reserved.
Publication Date: 2013
Journal of Coordination Chemistry (10290389) 66(24)pp. 4255-4267
A series of Ni(II) complexes of salen type Schiff base ligands were synthesized and characterized. The ligands were synthesized from the condensation of meso-1,2-diphenyle-1,2-ethylenediamine with salicylaldehyde (H2L1), 5-bromosalicylaldehyde (H2L2), 5-bromo-3-nitrosalicylaldehyde (H2L3), and 2′- hydroxyacetophenone (H2L4). The complexes were characterized by means of 1HNMR, IR, and UV-Vis spectroscopy and elemental analysis. Crystal structures of NiL3 and NiL4 were also determined by x-ray crystallography. Electrochemistry of the complexes was studied by means of cyclic voltammetry. Catalytic performance of the complexes was studied in the oxidation of cyclooctene using tert-butylhydroperoxide (TBHP) as oxidant. Various factors including solvent type, reaction temperature, time, catalyst amount, and substrate to oxidant ratio were optimized. Solvent free oxidation of cyclooctene with these catalysts was also studied. Increased catalytic activity and higher epoxide selectivity was achieved in solvent-free conditions. NiL4 with more electron donating substituents on the ligand was the most efficient oxidation catalyst. © 2013 © 2013 Taylor & Francis.
Publication Date: 2013
Polyhedron (02775387) 63pp. 68-73
In order to investigate the influence of intermolecular hydrogen bonds and the co-ligands [WS4]2 and Imt on the structures of copper complexes, two new compounds, [WS4Cu3I(tdmpp)] 4·2CH3CN (1) and [CuCl(Imt)·0.5tdmpp] 2·2(CH3)2CO (2), have been synthesized in one pot reactions. The reaction of CuI and (NH4)2WS4 with tdmpp (1,1,3,3-tetrakis(3,5-dimethyl-1-pyrazole)propane) (molar ratio = 3:1:1) in DMF/CH3CN (1:4; v/v) led to the formation of complex 1, while treatment of Imt (imidazolidine-2-thione) and CuCl with tdmpp (molar ratio = 2:2:1) in acetone formed complex 2. These complexes have been structurally characterized by X-ray crystallography, infrared spectroscopy and elemental analyses. Thermal analysis and UV-Vis spectroscopic analysis of complex 1 have also been undertaken. Complex 1 has a tetrameric structure which forms intermolecular C-H···S and C-H···I hydrogen bonds, resulting in a 2D polymeric structure. In this complex, the copper(I) atoms have two different geometries: trigonal planar (CuS 2I) and distorted tetrahedral (CuS2N2). In contrast, complex 2 has a dimeric structure in which the copper atoms are four-coordinate with a distorted tetrahedral CuN2SCl geometry. The dimeric molecules link to the oxygen atoms of uncoordinated acetone molecules through N-H···O hydrogen bonds. © 2013 Elsevier Ltd. All rights reserved.
Saljooghi a.s., A.S. ,
Amiri rudbari, H. ,
Nicolò, F. ,
Zahmati m., M. ,
Delavar mendi, F. Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(6)
The title compound, [Cu3(C7H3NO 4)4(C2H8N2) 2]·C2H8N2·4H 2O, was obtained by the reaction of copper(II) acetate dihydrate with pyridine-2,6-dicarboxylic acid (H2dipic) and ethylenediamine (en) in an aqueous solution. All of the CuII atoms in the trinuclear centrosymmetric title complex are six-coordinated in a distorted octahedral geometry with N2O4 and N4O2 environments for the outer and central CuII atoms, respectively. Various interactions, including numerous O - H⋯O and C - H⋯O hydrogen bonds and C - O⋯π stacking of the pyridine and carboxylate groups [O⋯centroid distances = 3.669 (2) and 3.668 (2) Å] are observed in the crystal structure.
Publication Date: 2012
Journal of Coordination Chemistry (10290389) 65(11)pp. 1872-1881
Two lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2, 2′-bipyridine (5,5′-dm-2,2′-bpy) and 4,4′-dimethoxy-2, 2′-bipyridine (4,4′-dmo-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H-NMR spectroscopy, thermal behavior, and X-ray crystallography. These complexes have formulas [Pb(5,5′-dm-2,2′-bpy)(NCS) 2] n (1) and [Pb(4,4′-dmo-2,2′-bpy)(NCS) 2] n (2). The coordination numbers of Pb II in 1 and 2 are four, PbN 4, with "stereo-chemically active" electron pairs and hemidirected coordination spheres. Considering PbS as weak bonds, 1 and 2 are 1- and 2-D coordination polymers, respectively. The supramolecular features in these complexes are guided/controlled by weak directional intermolecular interactions. © 2012 Taylor & Francis.
Mohammadi, M. ,
Akhbari, K. ,
Mazloomifar, A. ,
Ramazani, A. ,
Morsali, A. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Journal of Inorganic and Organometallic Polymers and Materials (15741443) 22(1)pp. 288-294
A new thallium(I) supramolecular polymer, [Tl 4(μ 3-2,4-cfp) 4] n (1) [2,4-Hcfp = 2-chloro-4-fluorophenol] (1) with disordered cubic cage structural unit has been synthesized and characterized. The single-crystal X-ray data of 1 shows four types of Tl I ions in the tetranuclear cubic cage unit with a coordination number three. In addition to an intra-cage thallophillic interaction, an inter-cage thallophillic interaction also exists and results in formation of 1D supramolecular polymer. Short contacts, Tl···H and Tl···C, make 1 a 3D supramolecular polymer. Short Tl···F and Tl···Cl secondary interactions also exist. Finally the Tl-ions attain O 3Tl1···C 6Tl 2, O 3Tl2···TlClF, O 3Tl3···Tl 2 and O 3Tl4···C 2TlH coordination spheres with a stereochemically 'active' electron lone pair of electrons on the metal ions. The thermal stability of 1 was studied by thermogravimetric and differential thermal analyses. Nanostructures of thallium(III) oxide were prepared from calcination of fine powders of 1 at 570 and 630 °C. These nanostructures were characterized by X-ray powder diffraction and scanning electron microscopy. © 2011 Springer Science+Business Media, LLC.
Bayraq, S.S. ,
Keykha, A. ,
Amiri rudbari, H. ,
Rahimizadeh, M. ,
Bakavoli, M. ,
Pourayoubi, M. ,
Nicolò, F. Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(8)
In the title compound, C5H5N3O, the isoxazole ring is essentially planar, with a maximum deviation of 0.007 (1) Å from the least-squares plane. The N atom of the amine group exhibits sp 2 character (sum of bond angles around this atom = 358°). In the crystal, mol-ecules are aggregated by two kinds of N-H⋯N hydrogen bonds into fused R 2 2(12) and R 6 6(26) rings, forming a slightly puckered two-dimensional array lying parallel to (101).
Saberikia, I. ,
Safaei, E. ,
Rafiee, M. ,
Cotic, P. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Journal of Molecular Structure (00222860) 1022pp. 109-116
A kind of new amine-chloro substituted phenol and its iron(III) complex has been prepared and characterized by spectroscopic, X-ray techniques and magnetic susceptibility studies. X-ray analysis revealed a binuclear complex, Fe 2(LTHF)3 in which two Fe(III) centers were surrounded by three ligands. The magnetic susceptibility indicates antiferromagnetic coupling between two iron centers through phenolate bridges. Voltammetric study of ligand (H2LTHF) and complex Fe 2(LTHF)3 revealed that the coordinated phenolate ligands undergo reversible two-electron oxidations with formation of coordinated phenoxyl radicals. It has seen that the oxidation of Fe 2(LTHF)3 comparing to its analog, Fe 2(LtBu)2 occurs at significantly higher potentials. It was attributed to the relationship between the radical stability with electronic and steric properties of ligands. Stability constants and thermodynamic parameters for the formation of Fe2(L THF)3 complex and the role of ligand coordination to iron center in phenoxyl radical stabilization has been investigated using anodic peaks potentials. © 2012 Elsevier B.V. All rights reserved.
Saberikia, I. ,
Safaei, E. ,
Kowsari, M.H. ,
Lee, Y. ,
Cotic, P. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Journal of Molecular Structure (00222860) 1029pp. 60-67
A new iron(III) complex of the glycine derivative of amine-chloro substituted phenol ligand (H3LGDC) has been prepared and characterized by IR, 1H NMR, UV-Vis spectroscopic techniques, cyclic voltammetry, ESI-MS and magnetic susceptibility studies. X-ray analysis reveals that in iron complex of FeLGDC the iron(III) center has a distorted trigonal bipyramidal coordination sphere and is surrounded by an amine nitrogen, a carboxylate, a water and two phenolate oxygen atoms. The DFT calculations with the UB3LYP/6-311++G- level optimized structure of the complex are in good agreement with experimental X-ray structural data. The variable-temperature magnetic susceptibility indicates that FeLGDC is the paramagnetic high spin iron(III) complex. It has been shown that electrochemical oxidation of this complex is ligand-centered due to the oxidation of phenolate to the phenoxyl radicals. This enzyme mimic utilized molecular oxygen in carrying out the oxidative cleavage of catechols with complete conversion at room temperature. © 2012 Elsevier B.V. All rights reserved.
Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(6)
The crystal structure of the title compound, (C6H 16N)2[CoCl4], is comprised of a tetrahedral [CoCl4]2- anion and two independent triethylammonium cations. The latter are featureless while the [CoCl4]2- anion exhibits typical Co - Cl bond lengths [2.2428 (15)-2.2847 (16) Å] and a Cl - Co - Cl angular range of 107.58 (6)-112.73 (7)°. In the crystal, N - H⋯Cl hydrogen bonds between the two crystallographically independent cations and the [CoCl4]2- anion generate discrete ion triplets. The two Co - Cl bonds involved in these interactions are slightly longer than the remaining two.
Publication Date: 2012
Journal of Coordination Chemistry (10290389) 65(19)pp. 3403-3412
A new 5-bromo-2-hydroxobenzaldehyde S-ethylisothiosemicarbazone hydroiodide free Schiff base (H 2L) is synthesized and a series of molybdenum(VI) complexes, Mo IVO 2LD, have prepared where D can be DMF, DMSO and pyridine. The compounds are characterized with molar conductance, FT-IR, 1H NMR, elemental analyses, and UV-Vis techniques. Structures of complexes are determined with X-ray analysis. All experimental results confirmed that H 2L is a tridentate bi-deprotonated ligand (ONN), coordinating through phenolic oxygen, azomethine nitrogen, and isothioamide nitrogen. The neutral complexes are distorted octahedral. © 2012 Copyright Taylor and Francis Group, LLC.
Publication Date: 2012
Polyhedron (02775387) 44(1)pp. 44-51
Two phenol-based unsymmetrical dinucleating macro-acyclic ligands (LH 2), which can contiguously accommodate two metal ions, one in a hexa-coordinate (N4O2) site and the other in a tetra-coordinate (N2O2) site, and their heterodinuclear complexes [ZnLMII]2+, where M = Cu or Ni, were prepared using a stepwise method. One of the ligand systems (L3H2) comprises an ethylenediamine link in the N4O2 compartment, whereas the other (L6H2) includes an 1,3-diaminopropane link. Both ligands contain two methyl arms attached to the nitrogen atoms in the N2O2 coordination site. The mononuclear complex of the type [ZnL3(H+)2]2+ has a C 2-symmetrical structure. When a second metal is incorporated, however, the resultant heterodinuclear complexes [ZnL3M II]2+ provide a non-symmetrical structure due to the occurrence of geometrical isomerization. In contrast, the mononuclear complex of the type [ZnL6(H+)2]2+ demonstrated a mixture of topological isomers and the structures of the resultant heterodinuclear complexes [ZnL6MII]2+, remained constant without a change in the structures with respect to the mononuclear complex. The origins of the structural variations are discussed. The structures of the complexes were studied by NMR, IR, UV-Vis spectroscopies and X-ray crystallography. © 2012 Published by Elsevier Ltd. All rights reserved.
Saljooghi a.s., A.S. ,
Amiri rudbari, H. ,
Nicolò, F. ,
Zahmati m., M. ,
Mendi, F.D. ,
Eshtiagh-hosseini, H. ,
Mirzaei, M. Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(8)
The asymmetric unit of the title complex, (C6H 8N)2[Cu(C7H3NO4) 2]·6H2O, contains half a copper(II)-dipicolinate complex located on a twofold rotation axis, one protonated aniline mol-ecule and three solvent water mol-ecules. The CuII atom is coordinated by four O atoms and two N atoms from two dipicolinate ligands in a distorted octa-hedral environment. In the crystal, the components are linked into a three-dimensional framework by inter-molecular O-H⋯O and N-H⋯O inter-actions.
Publication Date: 2012
Journal of Coordination Chemistry (10290389) 65(11)pp. 1970-1991
The dinucleating macrocyclic ligands (L 2a) 2- and (L 2b) 2- were prepared by [1:1] cyclic condensation of N,N′-dipropionitrile-N,N′-ethylene-di(5-methyl-3-formyl-2- hydroxybenzylamine or N,N′-dipropionitrile-N,N′-ethylene-di(5-bromo- 3-formyl-2-hydroxybenzylamine with 1,3-diaminopropane. The ligands include dissimilar N(amine) 2O 2 and N(imine) 2O 2 coordination sites sharing two phenolic oxygen atoms and containing two propionitrile pendant arms on the amine nitrogen atoms. A series of mono- and dinuclear complexes were synthesized and characterized on the basis of elemental analysis, molar conductance measurement, X-ray crystallography, IR, NMR, and UV-Vis spectroscopies as well as cyclic voltammetric measurements. During the cyclization copper(II) migrates from the N(amine) 2O 2 to the N(imine) 2O 2 coordination site and one of the propionitrile pendant arms is removed. The heterodinuclear complexes [ZnL 2Cu(OAc)] + were prepared by a transmetallation reaction. The characterization results showed that the two metal ions are bridged by two phenolic oxygen atoms and an acetate group, providing distorted five-coordinate geometries for both metals. © 2012 Taylor & Francis.
Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(2)
The title compound, C 9H 11NO 2, was obtained as an unexpected product in an attempt to synthesize a triazene ligand. The title mol-ecule is almost planar, with the formamide and eth-oxy groups oriented at 2.7 (3) and 12.9 (2)°, respectively, with respect to the mean plane of the benzene ring. In the crystal, mol-ecules are linked by inter-molecular N - H⋯O hydrogen bonds, forming a chain along the a axis. Weak C - H⋯π inter-actions with an H⋯π distance of 2.78 Å reinforce the crystal packing, resulting in a three-dimensional network.
Publication Date: 2012
Journal of Molecular Structure (00222860) 1026pp. 44-50
New organotin(IV) complexes, Ph 2SnL (1) and Me 2SnL (2), have been synthesized from reaction of corresponding diorganotin(IV) dichlorides with a Schiff base, 3-(2-hydroxy-5-methylphenylamino)-1,3- diphenylprop-2-en-1-one (H 2L), derived from condensation of 2-amino-4-methylphenol with dibenzoylmethane. The synthesized compounds have been investigated by elemental analysis and IR, 1H NMR, and 119Sn NMR spectroscopy. Spectroscopic studies show that the Schiff base acts as a tridentate dianionic ligand and coordinates via the nitrogen and phenolic and enolic oxygen atoms. The structures of H 2L and 2 have been also confirmed by X-ray crystallography. Schiff base exists as the keto-amine tautomeric form in solid state with two intramolecular hydrogen bonds of the NH⋯O type and also intermolecular hydrogen bonds of OH⋯O type that create a dimer. In the structure of 2, tin center is surrounded by two O and one N atoms from the ligand and two C atoms of methyl groups and the sixth coordination site is occupied by phenolic oxygen atom of another molecule, thus a dimeric molecule with a Sn 2O 2 four-membered ring is formed. The in vitro antibacterial activity of ligand and complexes has been evaluated against Gram-positive (Bacillus cereus and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. H 2L showed no activity but the diphenyltin(IV) complex exhibited good activities along with the standard antibacterial drugs. © 2012 Elsevier B.V. All rights reserved.
Rofouei, M.K. ,
Attar gharamaleki, J. ,
Fereyduni, E. ,
Aghaei, A. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Zeitschrift fur Anorganische und Allgemeine Chemie (00442313) 638(1)pp. 220-223
The reaction of [1, 3-bis(2-ethoxy)benzene]triazene, [HL], with Hg(SCN) 2 and Hg(CH 3COO) 2, resulted in the formation of the complexes [HgL(SCN)] (1) and [HgL 2]·CH 3OH (2). They were characterized by means of X-ray crystallography, CHN analysis, FT-IR, 1H NMR, and 13C NMR spectroscopy. The structure of compound 1 consists of two independent complexes in which the Hg II atoms are stacked along the crystallographic a axis to form infinite chains. Each Hg II atom is chelated by one L ligand and one SCN ligand, whereas in compound 2, the Hg II atom is surrounded by two L ligands. In addition, 1D chains formed by metal-π interactions are connected to each other by C-H⋯π stacking interactions in the structure of 1, which results in a 2D architecture. An interesting feature of compound 2 is the presence of C-H⋯π edge-to-face interactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Publication Date: 2012
Journal of Luminescence (00222313) 132(8)pp. 1860-1866
Two new macrocyclic systems (L 1, L 2+) containing two emissive naphthalene were synthesized and characterized. The macrocycles were studied by 1H NMR, 13C NMR, COSY, HMQC, DEPT, microanalysis and mass spectroscopy. The influence of metal cations Na, Cr 3+, Mn 2+, Fe 3+, Co 2+, Ni 2+, Cu 2+, Zn 2+, Cd 2+, and Hg 2+ on the spectroscopic properties of the macrocyclic systems in acetonitrile/DMF 9:1 (v/v) mixtures were investigated by means of absorption and emission spectrophotometry. The macrocycle L 1 was found to be as an effective fluorescence sensor for Zn 2+ ions. Zn 2+ and Cd 2+ ions show the most effects on the fluorescence intensity of L 2+. © 2012 Elsevier B.V. All rights reserved.
Publication Date: 2012
Inorganica Chimica Acta (00201693) 383pp. 250-256
Novel heterodinuclear complexes type [Zn IILM II] (ClO 4) 2 where L is a phenol-based ligand with two contiguous hexa-(N 4O 2) and tetra-coordination (O 2N 2) sites and M = Cu or Ni were prepared by a stepwise procedure. The prepared mono- and dinuclear complexes were characterized by elemental analysis, molar conductance measurements, X-ray crystallography, IR, NMR and UV-Vis spectroscopies. Characterization results confirmed the expected C 2 symmetrical geometry for the mononuclear zinc complex with trans-disposed pyridyl ligands. In contrast, the dinuclear complexes showed C 1 symmetrical structures so that, the Zn(II) ion resided in the six-coordination site with cis-disposed pyridyl ligands and the tetradentate compartment is occupied by M(II) ion in a square planar geometry. An unusual methyl elimination was occurred upon the introduction of the M(II) ions into the O 2N 2 coordination site of the mononuclear complex. The reason for these phenomena is an inherent structural feature of the dinucleating macroacyclic ligand that is discussed. © 2011 Elsevier B.V. All rights reserved.
Publication Date: 2012
Inorganic Chemistry Communications (13877003) 18pp. 15-20
A new oxovanadium(IV) Schiff base complex, V IVOL 2 (1), was prepared by the reaction of a bidentate Schiff base ligand L and VO(acac) 2 (L = N-salicylidin-2-chloroethylimine). The Schiff base ligand, L, and its oxovanadium(IV) complex, 1, were characterized by the elemental analysis (CHN) and FT-IR spectroscopy. In addition, 1H-NMR was employed for characterization of the ligand. The crystal structure of 1 was determined by the single crystal X-ray analysis. The Schiff base ligand L acts as a chelating ligand and coordinates via one nitrogen and one oxygen atom to the vanadium center. The complex 1 crystallizes in the monoclinic system, with space group P2 1/n, having one symmetry-independent V 4 + ion coordinating in an approximately square pyramidal N 2O 3 geometry by two imine nitrogen, two phenolato oxygen atoms from two Schiff base ligands in a square plane and one oxygen atom in an apical position. The catalytic activity of the complex 1 was tested in the epoxidation of cyclooctene. The results showed that the complex 1 was highly active and selective catalyst in optimized conditions in the epoxidation of cyclooctene. © 2012 Elsevier B.V. All rights reserved.
Rofouei, M.K. ,
Attar gharamaleki, J. ,
Melardi, M.R. ,
Hosseini, S.M. ,
Hosseinzadeh, F. ,
Peyman, M. ,
Ghannadan, A. ,
Notash, B. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Polyhedron (02775387) 44(1)pp. 138-142
The synthesis of two [Hg(L1)2] and [Hg(L2)2] complexes using asymmetric triazenes as ligands are reported. The triazene ligands are substituted with cyano and chloride groups in the ortho positions of the aryl rings (where HL1 and HL2 are 1-(2-ethoxyphenyl)-3-(2-cyanophenyl) triazene and 1-(2-ethoxyphenyl)-3-(2-chlorophenyl) triazene, respectively). These complexes were prepared by the reaction of corresponding triazenes with Hg(NO3)2 and were characterized by FT-IR, NMR, elemental and single crystal X-ray analyses. Both triazene ligands were found to deprotonate on coordination and act as tridentate chelating ligands forming distorted N4O2 octahedral geometry around HgII atoms. Hydrogen bonds, π⋯π and C-H⋯π stacking interactions help to the stabilization of the resulted frameworks. © 2012 Published by Elsevier Ltd. All rights reserved.
Publication Date: 2012
Chinese Journal of Chemistry (16147065) 30(8)pp. 1873-1880
The syntheses of three mixed ligand chelate copper(II) complexes of the type [Cu(L)(acac)(H 2O)]BPh 4 where acac=acetyleacetonate; L=N,N-dimethyl,N′-benzylethane-1,2-diamine (L 1), N,N-dimethyl, N′-2-methylbenzylethane-1,2-diamine (L 2) or N,N-dimethyl,N′-2-chlorobenzylethane-1,2-diamine (L 3) are reported and characterized by elemental analyses, spectroscopic and molar conductance measurements. The X-ray structure of complex 1 shows that the central copper atom is placed in a distorted square pyramidal geometry made by acac and diamine chelate in the base and a H 2O molecule on the apex. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Calculations of SMLR (stepwise multiple linear regression) method was utilized to find the best model explaining the observed solvatochromic behavior and showed that among different solvent parameters, donor number (DN) is a dominant factor responsible for the shift in the d-d absorption band of the complexes to the lower wavenumber with increasing its values. The importance of substituent effect in diamine ligand on the spectral and SMLR measurements is also discussed. © 2012 SIOC, CAS, Shanghai & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Publication Date: 2012
Journal of Coordination Chemistry (10290389) 65(10)pp. 1712-1723
The Schiff base, 4-(2-hydroxynaphthalen-3-ylamino)pent-3-en-2-one (H 2L) and its diphenyltin complex have been synthesized and characterized by elemental analysis and FT-IR, 1H, or 119Sn NMR spectroscopy. The structures of free ligand and complex have been confirmed by single-crystal X-ray diffraction. In the structure of H 2L, enolic proton is transferred to imine nitrogen and there is an intramolecular hydrogen bond between amine and carbonyl group. There are also 1-D intermolecular hydrogen-bonded chains with π-π stacking between chains. SnPh 2L is crystallized in the Pca2(1) orthorhombic space group with four molecules in an asymmetric unit cell. The geometry around tin is a highly distorted trigonal bipyramid with Schiff base completely deprotonated and coordinated tridentate to tin via phenolic and enolic oxygen atoms in axial and imine nitrogen in equatorial positions. The results of X-ray diffraction were also compared with density functional theory calculations. These calculations also confirm the keto-amine tautomeric form for Schiff base in solid phase. The in vitro antibacterial activities of ligand and complex have been evaluated against Gram-positive (Bacillus cereus and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacteria. H 2L showed no activity but the diphenyltin(IV) complex exhibited good activities along with the standard antibacterial drugs. © 2012 Taylor & Francis.
Rofouei, M.K. ,
Ghalami, Z. ,
Attar gharamaleki, J. ,
Ghoulipour, V. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Zeitschrift fur Anorganische und Allgemeine Chemie (00442313) 638(5)pp. 798-803
The title ligand, [1-(2-methoxyphenyl)-3-(4-chlorophenyl)]triazene, HL (1), was prepared. In a reaction with Hg(NO 3) 2 it forms the complex [Hg(C 26H 22Cl 2N 6O 2)], [HgL 2] (2). Both compounds were characterized by means of X-ray crystallography, CHN analysis, FT-IR, 1H NMR, and 13C NMR spectroscopy. In the structure of compound 1, two independent fragments are present in the unit cell. They exhibit trans arrangement about the -N=N- double bond. The dihedral angles between two benzene rings in both fragments are 4.36 and 18.79 Å, respectively. Non-classic C-H⋯N hydrogen bonding and C-H⋯π interactions form a layer structure along the crystallographic ab plane [110]. In compound 2, the Hg II atom is hexacoordinated by two tridentate [1-(2-methoxyphenyl)-3-(4-chlorophenyl)] triazenide ligands through a N 2O 2 set. In addition, in the structure of 2, monomeric complexes are connected to each other by C-H⋯π stacking interactions, resulting in a 2D architecture. These C-H⋯π edge-to-face interactions are present with H⋯π distances of 3.156 and 3.027 Å. The results of studies of the stoichiometry and formation of complex 2 in methanol solution were found to support its solid state stoichiometry. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Dolatyari, L. ,
Bayraq, S.S. ,
Sharifi, S. ,
Ramazani, A. ,
Morsali, A. ,
Amiri rudbari, H. Publication Date: 2012
Acta Crystallographica Section E: Structure Reports Online (16005368) 68(10)
The asymmetric unit of the title salt, C4H12N +.C8H5O4-, contains one half of a tetramethylammonium cation and one half of a hydrogen terephthalate monoanion. The N atom of the ammonium cation lies on a twofold rotation axis and the centre of mass of the terephthalate anion is on a centre of inversion. In the crystal, the centrosymmetric terephthalate ions are linked by a very short symmetric O - H·O hydrogen bond [O·O = 2.4610 (19) Å] into a one-dimensional polymeric chain along [11̄2]. The tetramethylammonium cations and terephthalate anions are then connected through a pair of bifurcated acceptor C - H̄O hydrogen bonds, generating a three-dimensional supramolecular network. The carboxylate groups at both ends of the terephthalate anion are charge-shared with an equal probability of 0.5.
Pourayoubi, M. ,
Jasinski, J.P. ,
Shoghpour bayraq, S. ,
Eshghi, H. ,
Keeley, A.C. ,
Bruno, G. ,
Amiri rudbari, H. Publication Date: 2012
Acta Crystallographica Section C: Crystal Structure Communications (16005759) 68(10)
In the phospho-ric triamides N,N,N′,N′-tetrabenzyl-N″-(2- chloro-2,2-difluoroacetyl)phospho-ric triamide, C30H 29ClF2N3O2P, (I), N,N,N′,N′-tetrabenzyl-N″-(3-fluoro-benzo-yl)phospho-ric triamide, C35H33FN3O2P, (II), and N,N,N′,N′-tetrabenzyl-N″-(3,5-difluoro-benzo-yl)phospho-ric triamide, C35H32F2N3O2P, (III), the tertiary N atoms of the dibenzyl-amido groups have sp 2 character with minimal deviation from planarity. The sums of the three bond angles about the N atoms in (I)-(III) deviate by less than 8° from the planar value of 360°. The geometries of the tertiary N atoms in all phospho-ric triamides with C(O)NHP(O)[N]2 skeletons deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380-388] have been examined and the bond-angle sums at the two tertiary N atoms (SUM1 and SUM2) and the parameter SUM (= SUM1 - SUM2) considered. It was found that in compounds with a considerable ΔSUM value, the more pyramidal N atoms are usually oriented so that the corresponding lone electron pair is anti with respect to the P=O group. In (I), (II) and (III), the phosphoryl and carbonyl groups, separated by an N atom, are anti with respect to each other. In the C(O)NHP(O) fragment of (I)-(III), the P - N bond is longer and the O - P - N angle is contracted compared with the other two P - N bonds and the O - P - N angles in the molecules. These effects are also seen in analogous compounds deposited in the CSD. Compounds with [C(O)NH]P(O)[N]X (X ≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been considered here. Also, com-pounds with a [C(O)NH]2P(O)[N] fragment have not been reported to date. In the crystal structures of all three title compounds, adjacent molecules are linked via pairs of P=O⋯H - N hydrogen bonds, forming dimers with C i symmetry. © 2012 International Union of Crystallography.
Publication Date: 2012
Polyhedron (02775387) 45(1)pp. 9-14
With the aim of discovering novel urease inhibitors, six new mononuclear complexes of five-coordinated Zn(II) bromide and iodide with terpyridine derivatives have been synthesized and their solid state structures were characterized by X-ray crystallography. Among these complexes, the zinc complexes bearing an electron withdrawing aryl group at the 4′-position show medium urease inhibitory activities, with IC50 values much lower than those of previously reported zinc species, at concentrations lower than 100 mM. © 2012 Elsevier Ltd. All rights reserved.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(12)
In the title compound, [Cu(C24H27N4O 3)]ClO4, the CuII atom has a distorted square-planar coordination geometry and is surrounded by an N3O donor set composed of a secondary amine N, a primary amine H, an imino N and a naphthalen-2-olate O atom. An intramolecular N - H⋯O hydrogen bond occurs. In the crystal, molecules are held together by intermolecular N-H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(12)
The title Schiff base compound, C33H30N 4O4·H2O, adopts an E configuration with respect to each C=N double bond. In the molecule, there are naphthoxide anions and the protonated imino N atoms. intramolecular N-H⋯O hydrogen bonds lead to the formation of approximately planar (maximum deviation 0.029 Å for H atom) six-membered rings.. In the crystal, molecules are linked by O-H⋯O and N-H⋯O hydrogen bonds as well as C - H⋯O contacts, leading to the formation of a three-dimensional network..
Foroughian, M. ,
Foroumadi, A. ,
Notash, B. ,
Bruno, G. ,
Amiri rudbari, H. ,
Aghabozorg, H. Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(12)
The asymmetric unit of the title proton-transfer compound, C 5H8N3 +·C7H 4NO4 -, consists of one mono-deprotonated pyridine-2,6-dicarb-oxy-lic acid as anion and one protonated 2,3-diaminopyridine as cation. The crystal packing shows extensive O-H⋯O, N-H⋯O and N - H⋯N hydrogen bonds. Thre are also several π-π interactions between the anions and also between the cations [centriod-centroid distances = 3.6634 (7), 3.7269 (7), 3.6705 (7) and 3.4164 (7) Å].
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(12)
The title compound, C14H14N4O3, exhibits a trans geometry about the N=N double bond in the triazene unit. The molecule is approximately planar (r.m.s. deviation = 0.044 Å for all non-H atoms). An intramolecular N-H⋯O hydrogen bond occurs. In the crystal, C-H⋯N hydrogen bonds lead to the formation of dimers which are, in turn, connected to each other by C-H⋯O hydrogen bonds, forming infinite chains of R2 2(8) graph-set motif.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(10)
The asymmetric C atom in the title compound, 21H 17 BrClNO, is in a slightly distorted tetra-hedral environment and the NH unit adopts a gauche orientation with respect to the CO group. In the crystal, pairs of inter-molecular N-H⋯O hydrogen bonds form centrosymmetric dimers.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(7)
The title compound, C 13H 12ClN 3O, exhibits a trans geometry about the N=N double bond in the solid state. The dihedral angle between the rings is 22.20 (8)°. Inter-molecular N - H⋯O hydrogen bonds between the amine and meth-oxy groups lead to the formation of a chain-like polymer along the c axis with a C(6) graph set. There is also weak non-classical C - H⋯N hydrogen bonds involving an aromatic C - H group and a diazenyl N atom, which connect the chains into a two-dimensional framework. © Rofouei et al. 2011.
Publication Date: 2011
Inorganic Chemistry (00201669) 50(22)pp. 11653-11666
A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N]2- [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η3-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η3-allyl)PdCl]2 in chloroform. At low temperature (20 °C), the bimetallic complexes [(η3-allyl)Pd] 2(μ-dialkyldithiooxamidate κ-N,N′ Pd, κ-S,S′ Pd′) (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η3-allyl)Pd] 2(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N′, S′ Pd′) (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η3-allyl)Pd(N^N) frame of kinetic compounds or in the (η3-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N]2-, when engaged in a κ-N,S Pd, κ-N′,S′ Pd′ coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η3- allyl)Pd]2(μ-diethyldithiooxamidate κ-N,S Pd, κ-N′,S′ Pd′), [(η3-allyl)Pd] 2(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N′,S′ Pd′), and [(η3-allyl)Pd] 2(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N′ Pd, κ-S,S′ Pd′) are reported. © 2011 American Chemical Society.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(9)
In the title compound, [Cu(C 4H 12N 2O) 2](NO 3) 2, the central Cu II atom has a distorted octahedral coordination geometry and is surrounded by four N atoms and two O atoms from the two inversionrelated 2-(2-aminoethylamino)-ethanol ligands. In the crystal, molecules are held together by intermolecular O - H⋯O and N - H⋯O hydrogen bonds, leading to the formation of a threedimensional network.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(6)
In the title molecule, C17H20NO3P, the P atom is bonded in a distorted tetra-hedral environment. The dihedral angle between the two phenyl rings is 23.52 (10)°. The phosphoryl and N-H groups are anti with respect to one another. The -CH2-CH2-CH 2-CH2- sequence of atoms in the cyclopentyl ring is disordered over two sets of sites with refined occupancies of 0.574 (10) and 0.426 (10). In the crystal, molecules are linked via N-H⋯O=P hydrogen bonds to form extended chains along [010].
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(2)
In the title Schiff base compound, C17H22N 2O2S2, which adopts an E configuration with respect to the imine C=N double bond, the C=N and N -C bond distances are 1.2789 (16) and 1.4546 (16) Å, respectively. In the molecule there are intramolecular O -H⋯N and N -H⋯S hydrogen bonds, and the CH=N -C substituent is almost coplanar with the benzene ring [C -N -C -C torsion angle = -178.80 (11)°]. The crystal packing is stabilized by intermolecular C -H⋯O and C -H⋯π interactions involving the aromatic ring.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(11)
In the title compound, C21H21FN3O 2P, the NH and P(=O) groups of the C(=O)NHP(=O) fragment are in a syn arrangement with respect to each other, as are the two amide H atoms of the two CH3-4-C6H4-NH moieties. In the crystal, mol-ecules are linked through N - H⋯O(=P) and N - H⋯O(=C) hydrogen bonds, forming R22(8) and R2 2(12) rings, which are arranged in chains parallel to [010]. © Pourayoubi et al. 2011.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(6)
In the title compound, C17H24N3O 3PS, the P and the S atoms are each in a distorted tetra-hedral environment and the N atoms display sp 2 character. The phosphoryl group and the NH unit are anti with respect to one another. The dihedral angle between the mean planes of the benzene rings is 31.08 (8)°. The crystal packing is stabilized by N - H⋯O hydrogen bonds, forming an extended chain parallel to the b axis.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(11)
In the title compound, C21H33FN3O 2P, the P atom has a distorted tetra-hedral environment and the N atoms display geometries consistent with a model of sp 2 hybridization (with bond-angle sums for the tertiary N atoms of 357.8 and 358.7°). The phosphoryl and carbonyl groups are anti with respect to each other. In the crystal, inversion dimers linked by pairs of N - H⋯O hydrogen bonds generate R22(8) loops. © Pourayoubi et al. 2011.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(4)
The asymmetric unit of the title proton-transfer compound, C 5H16N2 2+·2C 7H4NO4-·H2O, consists of two mono-deproton-ated pyridine-2,6-dicarboxylic acid molecules as anions, viz. (py-2,6-dcH)-, one diprotonated N 1,N 1-diMethylpropane-1,2-diamine molecule as a cation, viz. (dmpdaH 2)2+, and one water molecule. The crystal packing shows extensive O - H⋯O, N - H⋯O, N - H⋯N and O - H⋯N and weak intermolecular C - H⋯O hydrogen bonds. These inter-actions link the (dmpdaH2)2+ cation, the (py-2,6-dcH)- anions and water molecule and play an important role in the stabilization of crystal packing.
Publication Date: 2011
Synthetic Communications (00397911) 41(4)pp. 528-532
A novel 23-membered heptadentate N3O4 Schiff base ligand has been prepared by [1+1] cyclocondensation of 1,2-bis(2′- aminophenoxy)-4-t-butylbenzene with 2,6-bis(2- formylphenoxymethyl)pyridine by a nontemplate procedure. Treatment of L1 with NaBH4 in EtOH/CHCl 3 gave the di-amine macrocycle L2. © 2011 Taylor & Francis Group, LLC.
Publication Date: 2011
Acta Crystallographica Section E: Structure Reports Online (16005368) 67(7)
In the title compound, (C 3H 12N 2)[Hg(C 7H 3NO 4) 2]· 2H 2O, the Hg II ion is coordinated by four O and two N atoms of two pyridine-2,6-dicarboxyl-ate (pydc) ligands in a distorted octa-hedral environment. The structure contains two uncoordinated water mol-ecules. In the crystal, N - H⋯O, O - H⋯O and weak C - H⋯O hydrogen bonds and π-π stacking inter-actions between the pyridine rings of the pydc ligands, with a centroid-centroid distance of 3.4582 (18) Å, stabilize the structure. © Agah et al. 2011.
Publication Date: 2011
Polyhedron (02775387) 30(6)pp. 1027-1034
Solvatochromic mixed-chelate copper(II) complexes, [Cu(Cl-acac)(diamine)]X (where Cl-acac = 3-chloroacetylacetonate ion, diamine = N,N′-dimethyl, N′-benzyl-1,2-diaminoethane and X = B(Ph)4-, PF 6-, BF4- and ClO4 -), have been prepared. The complexes were characterized on the basis of elemental analysis, molar conductance, UV-Vis and IR spectroscopies. Single crystals of [Cu(Cl-acac)(diamine)(H2O)]PF6, complex 2, were also characterized by X-ray diffraction. The influence of the solvent polarity and counter ions on the νmax values of the d-d bands of the complexes have been investigated by means of visible spectroscopy. All the complexes demonstrated negative solvatochromism. A multi-parametric equation has been utilized to explain the solvent effect on the d-d transition of the complexes using SPSS/PC software. The stepwise multiple linear regression (SMLR) method demonstrated that the donor power of the solvent plays the most important role in the solvatochromism of the compounds. The relative donor power of the anions X was determined by visible spectra in the solvent dichloromethane. © 2011 Elsevier Ltd. All rights reserved.
Publication Date: 2011
Inorganica Chimica Acta (18733255) 366(1)pp. 290-297
Four new symmetric mixed-chelate dinuclear complexes type [Cu 2(L)2(TAE)]X2, where TAE = tetraacetylethane; L = N,N-dimethyl-N′-benzylethylenediamine (L1) or N,N′-dibenylethylenediamine (L2); X = ClO4 or BPh4 have been synthesized and characterized on the bases of elemental analysis, spectroscopic and conductance measurements. The X-ray crystal analysis of [Cu2(L1)2(TAE)](ClO 4)2 demonstrated that the two copper(II) ions are not equivalent. The axial position of the first copper is occupied by a ClO 4- ion with a square pyramidal geometry whereas; the second copper ion resides in an octahedral environment determined by two perchlorate anions. However, in solution, the perchlorate ions are driven out by solvent molecules leading to their solvatochromism. The solvatochromism of the complexes were investigated in various organic solvents and also were compared with those of the corresponding mononuclear complexes [Cu(L)(acac)]ClO 4. Their solvatochromism were also investigated with different solvent parameters models using stepwise multiple linear regression (SMLR) method. The results suggested that the DN parameter of the solvent has the dominate contribution to the shift of the d-d absorption band of the complexes. The results demonstrated that the complexes with counter ions of BPh4 are more solvatochromic in very weak donor solvents owing to their disinclination in ion-pair formation. © 2010 Elsevier B.V. All rights reserved.
Publication Date: 2010
Acta Crystallographica Section E: Structure Reports Online (16005368) 66(9)
In the title compound, [Hg(C14H13N4O 3)2], the central Hg atom (site symmetry 2) is six-coordinated by two tridentate 1-(2-eth-oxy-phenyl)-3-(4-nitro-phenyl) triazenide ligands through two N and one O atoms. The mononuclear complex molecules are connected into two parallel chains by inter-molecular C-H⋯O hydrogen-bonding inter-actions. These chains are connected to each other by face-to-edge C-H⋯π inter-actions between the CH of the ethoxy groups and the aromatic rings, resulting in a two-dimensional architecture in the ac plane.
Publication Date: 2010
Synthetic Communications (15322432) 40(10)pp. 1486-1491
Two novel macrocyclic tetra-imine-diphenol Schiff base (H2L 1 and H2L2) were synthesized by [2+2] cyclocondensation of ortho-aminophenyl diamines [1,2-bis(2'-aminophenoxy)benzene (I) and 1,2-bis(2'-aminophenoxy)-4-t-butylbenzene (II)] with 2,6-diformyl-4-methylphenol. Two novel tetra-amine-diphenol macrocycles (H 2L3 and H2L4) have been obtained by reduction of the imine analogs with NaBH4 in MeOH/CHCl3. Copyright © Taylor & Francis Group, LLC.
Publication Date: 2010
Journal of Coordination Chemistry (10290389) 63(23)pp. 4165-4176
Two new potentially octadentate N2O6 Schiff-base ligands 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy) phenoxy)phenylimino)methyl)-6-methoxyphenol H2L1 and 2-((E)-(2-(2-(2-((E)-2-hydroxy-3-methoxybenzylideneamino)phenoxy) -4-tert-butylphenoxy)phenylimino)methyl)-6-methoxyphenol H2L 2 were prepared from the reaction of O-Vaniline with 1,2-bis(2'-aminophenoxy)benzene or 1,2-bis(2'-aminophenoxy)-4-t-butylbenzene, respectively. Reactions of H2L1 and H2L 2 with copper(II) and zinc(II) salts in methanol in the presence of N(Et)3 gave neutral [CuL1] 0.5CH2Cl2, [CuL2], [ZnL1] 0.5CH2Cl2, and [ZnL2] complexes. The complexes were characterized by IR spectra, elemental analysis, magnetic susceptibility, ESI-MS spectra, molar conductance (m), UV-Vis spectra and, in the case of [ZnL1] 0.5CH2Cl2 and [ZnL2], with 1H- and 13C-NMR. The crystal structure of [ZnL1] 0.5CH2Cl2 has also been determined showing the metal ion in a highly distorted trigonal bipyramidal geometry. The electrochemical behavior of H2L2 and its Cu(II) complex, [CuL2], was studied and the formation constant of [CuL2] was evaluated using cyclic voltammetry. The logarithm value of formation constant of [CuL 2] is 21.9. © 2010 Taylor & Francis.
Publication Date: 2010
Inorganic Chemistry (00201669) 49(20)pp. 9236-9246
The meso-dithioxamide H-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl) ethyl)-H (H2-mesoDTO) bonds [(η6-p-cymene)chlorido- ruthenium(II)]+ or [(η3-allyl)-palladium(II)] + fragment and provides the Cs symmetrical complexes [(η6-p-cymene)ClRu(H-mesoDTO κ-S,S Ru)] (1) and [(η3-allyl)palladium(H-mesoDTO κ-S,S Pd)] (2). These complexes are pseudochiral, and each of them exists as a mixture of two symmetrical meso forms. The improper symmetry of [(η3-allyl) palladium(H-mesoDTO κ-S,S Pd)] has been broken in two different ways: (i) by changing the symmetrical allyl moiety with a η3-crotyl frame or (ii) by substituting the residual amidic hydrogen in the dithiooxamidate ligand with aM(PR3)Cl+fragment (M = Pd or Pt and PR 3 = triorganophosphine). As aconsequence, a chiral plane is added to the pseudochiral palladium center, and two pairs of enantiomers are formed in each case. Furthermore, [(η6-p-cymene)chlorido-ruthenium(II)] + and [(η3-allyl)-palladium(II)]+ fragments have been joined by means of the binucleating meso-dithiooxamidate ligand in a κ-S,S Ru κ-N,N Pd coordination mode. The resulting C s-symmetrical complex [(η6-p-cymene)ClRu(μ-mesoDTO κ-S,S Ru κ-N,N Pd)Pd(η3-allyl)] (8) possesses two pseudochiral metal centers, and it is therefore a mixture of four isomeric meso forms. All of these isomers in a chloroform solution interconvert in that both palladium and ruthenium invert their configurations. A mechanism of epimerization for both palladium and ruthenium is proposed. The absolute configurations of pseudochiral palladium in [(η3-allyl)(c)- Pd(μ-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl) κ-N,N (c)-Pd κ-S,S (A,C)-Pd)(A,C)-Pd(trinpropyl-phosphine)Cl] (6) and of pseudochiral palladium and ruthenium in [(η3-allyl)(c)- Pd(μ-((R)-1-(1-phenyl)ethyl)-NSC-CSN-((S)-1-(1-phenyl)ethyl) κ-N,N (c)-Pd κ-S,S(s)-Ru)(s)-Ru(η6-isopropyltoluene)Cl] (8) are provided. A suitable stereochemical notation is proposed for bimetallic complexes containing pseudochiral centers in either a chiral or an achiral environment. © 2010 American Chemical Society.
Publication Date: 2009
Journal of Chemical Research (03082342) (6)pp. 361-365
themacrocyclic, hexadentate (N4O2 and N 2O4) Schiff base ligands, 1,2-bis(2'-nitrophenoxy)benzene, 1,2-bis (2'-nitrophenoxy)-4-t-butylbenzene), 1,2-bis(2'-aminophenoxy)benzene and 1,2-bis Zinc(II), copper(II) and cobalt have been characterised by spectroscopy and elemental analysis.
Publication Date: 2009
Transition Metal Chemistry (1572901X) 34(8)pp. 835-839
Three new potentially hexadentate N4O2 Schiff-base ligands (H2L1, H2L2 and H 2L3) were prepared from the reaction of the polyamines N,Ń-bis(2-aminophenyl)-1,2-ethanediamine (L1), N,Ń-bis(2-aminophenyl)-1,3-propanediamine (L2) and N,Ń-bis(2-aminophenyl)-1,4-butanediamine (L3), respectively with salicylaldehyde. Reaction of the Schiff bases with Ni(II) salts in the presence of N(Et)3 gave the neutral complexes [NiL4], [NiL5] and [NiL6]. Ni(II) complexes of the polyamines were also prepared. One of complexes [Ni(L1)(MeCN)2](ClO 4)2•MeCN has been characterized through X-ray diffraction methods. © 2009 Springer Science+Business Media B.V.
Publication Date: 2009
Tetrahedron Letters (00404039) 50(2)pp. 169-171
N,N′-Bis(2-aminophenyl)-1,2-ethanediamine is synthesized from 1,2-diaminoethane and 1-chloro-2-nitrobenzene in the presence of sodium carbonate and the product reduced by zinc dust and ammonium chloride. A novel stable dication is synthesized by reaction of N,N′-bis(2-aminophenyl)-1,2-ethanediamine and 2-pyridinecarboxaldehyde in the presence of manganese chloride in methanol. The X-ray structural analysis shows formation of the dication. © 2008 Elsevier Ltd. All rights reserved.
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