24.12.2010
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24.12.2010


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Inorganica Chimica Acta
Volume 365, Issue 1, 15 January 2011, Pages 377-383







Two new organic–inorganic hybrid materials based on the polyoxotungstoaluminates





Tianzhan Zhanga, Ying LuCorresponding Author Contact Information, a, Weilin Chena, Xin Wanga, Shuang Yaoa, Zhiming Zhanga and Enbo WangCorresponding Author Contact Information, a, E-mail The Corresponding Author






a Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Renmin Street No. 5268, Changchun, Jilin 130024, PR China





Received 18 May 2010; 


revised 20 September 2010; 


accepted 27 September 2010. 


Available online 8 October 2010.









Abstract



Two new organic–inorganic hybrid compounds, {[Cu(2,2′-bipy)2]2(Hbpy)[α-AlW12O40]}·H2O (1) and {[H2en][CuI(4,4′-bipy)]3(α-AlW12O40)}·4H2O (2) (2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine, py = pyridine, en = ethylene dimine) based on Keggin-type α-[AlW12O40]5− polyoxoaions and transition-metal organoamine subunits, have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TG), and single-crystal X-ray diffraction. In addition, the electrochemical properties and photocatalytic activity of compound 1 were studied. The structural analysis reveals that 1 shows a 1D infinite chain structure constructed from [α-AlW12O40]5− polyoxoanions and {[CuII(2,2′-bipy)2][CuII(2,2′-bipy)(py)]}4+ fragments, in which the remarkable aspect is that [α-AlW12O40]5− polyoxoanion is modified in a fascinating symmetrical mode. Compound 2 displays an unprecedented 2D extended structure constructed from [α-AlW12O40]5− polyoxoanions and 4,4′-bipy-CuI-4,4′-bipy linear chains, in which three – chain belts formed by three linear chains arranged Cu parallel connect alternately with [α-AlW12O40]5− polyoxoanions. As far as we know, compounds 1 and 2 represent the first 1D and 2D extended hybrid materials constructed from 3d transition metals and polyoxotungstoaluminates linked through covalent bonds.









Graphical abstract



Two new organic–inorganic hybrid compounds with Keggin-type α-[AlW12O40]5− polyoxoaion and transition-metal organoamine subunits, namely, {[Cu(2,2′-bipy)2]2(Hbpy)[α-AlW12O40]}·H2O (1) and {[H2en][CuI(4,4′-bipy)]3(α-AlW12O40)}·4H2O (2) have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis (TG), and single-crystal X-ray diffraction. The electrochemical properties and photocatalytic activity of compound 1 have been investigated.






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