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Journal of Coordination Chemistry
Year: 2010  |  Volume: 63  |  Issue: 2  |  Page No.: 196 - 205

Two organic-inorganic hybrids based on polyoxometalates: synthesis, crystal structure, and characterization

Feng Yao, Fan-Xia Meng, Ya-Guang Chen and Chun-Jing Zhang    

Abstract: Two new Keggin- and Wells-Dawson-type polyoxometalate-based organic-inorganic hybrid copper-organonitrogen complexes have been synthesized under hydrothermal conditions: [CuI(4,4'-bpy)]2[H2SiW12O40] ⋅ 2H2O (4,4'-bpy = 4,4'-bipyridine) (1) and {[Cu1(4,4´-bpy]3 [Cu11(en)2]2[As2 Wv3W15 O62]}2 [Cu13(4,4´-bpy)3(H2O)2](HO).4H2O(2)(en =ethylenediamine), and characterized by elemental analysis, IR spectra, TGA, XRD, and single crystal X-ray diffraction. In 1, [Cu(4,4'-bpy)]+ cations form polymeric chains [Cu(4,4´-bpy)]n+n  and a weak Cu-O linkage makes the anions situate between two chains, forming an infinite 1-D ladder-chain structure. Such 1-D ladder-chains are further interconnected via hydrogen bonding into a 3-D supramolecular framework. Compound 2 with covalently bonded 3-D structure consists of saturated Wells-Dawson tungstoarsenate polyoxoanions and copper complexes with two types (rigid and flexible) of ligands. The polyoxoanion has the highest connectivity for Wells-Dawson tungstoarsenate polyoxoanion coordination polymers to date. XPS spectra indicate that three W atoms in the Dawson unit were reduced and that there coexist CuI and CuII in 2.

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