Inorganic–organic hybrid materials with different dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanion clustersElectronic supplementary information (ESI) available: Diagrams of the structures, FT-IR spectroscopy, TGA curve for 1–6 and electrochemistry for 1, 2, 5 and 6. See DOI: 10.1039/b717376h

Inorganic–organic hybrid materials based on Keggin polyoxometalate building blocks combined with CuII/CuI and flexible fluconazole ligand [1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]methanol] (Hfcz) have been obtained by hydrothermal methods, namely, [CuII2(Hfcz)4(SiW12O40)]·3H2O (1), [CuII4(fcz)4(H2O)4(SiMo12O40)]·6H2O (2), [CuII2(fcz)2][CuII4(fcz)4(SiW12O40)][CuII2(fcz)2(H2O)2(SiW12O40)]·6H2O (3), (Et3NH)2[CuI2(Hfcz)2(SiW12O40)]·2H2O (4), (Et3NH)2[CuI2(Hfcz)2(SiW12O40)]·H2O (5) and [CuI4(Hfcz)4(SiMo12O40)] (6). Their structures have been determined by single-crystal X-ray diffraction analyses, and the compounds are further characterized by elemental analyses, IR spectra and thermogravimetric (TG) analyses. In 1, Cu(ii) cations are bridged by fluconazole ligands to form a 3D lvt coordination polymeric network, which is connected by (SiW12O40)4− anions to form a complicated 3D (4,6)-connected framework with the topology of (42·64)(46·67·82)2. In 2, two fcz− anions chelate two Cu2+ cations to form a [Cu(fcz)]22+ dimer, which is bridged by (SiW12O40)4− polyanions to generate a 2D (4,4) grid. Compound 3 is formed by three types of co-crystallizing subunits including a dimer [Cu(fcz)]22+, a dumbbell molecule [Cu4(fcz)4(SiW12O40)] and an infinite chain {[Cu2(fcz)2(H2O)2(SiW12O40)]2−}∞. In compounds 4 and 5, Hfcz ligands link Cu+ cations to generate 1D coordination polymeric units, and (SiW12O40)4− polyanions connect these metal–organic units to form two types of (63) sheets which are topological isomerism. In compound 6, (SiMo12O40)4− polyanions fixed in CuI–Hfcz square rings are further extended into a 2D sheet via linking CuI atoms of different rings. By carefully inspection of the structures of 1–6, it is believed that various transition-metal organic units and Keggin polyanions with different coordination modes are important for the formation of the different structures. In addition, electrochemical behaviors of compounds 1, 2, 5 and 6 have been investigated. [ABSTRACT FROM AUTHOR]