3D Supramolecular Polymer Constructed from Agostic, Polyhapto and Thallophillic Interactions: A New Precursor for Preparation of Tl 2O 3 Nanoflowers

Abstract

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.