Issue 15, 2008

Inorganic–organic hybrid materials with different dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanion clusters

Abstract

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.

Graphical abstract: Inorganic–organic hybrid materials with different dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanion clusters

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2007
Accepted
07 Jan 2008
First published
18 Feb 2008

Dalton Trans., 2008, 2015-2025

Inorganic–organic hybrid materials with different dimensions constructed from copper–fluconazole metal–organic units and Keggin polyanion clusters

S. Li, Y. Lan, J. Ma, J. Yang, J. Liu, Y. Fu and Z. Su, Dalton Trans., 2008, 2015 DOI: 10.1039/B717376H

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