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Combination of Lacunary Polyoxometalates and High-Nuclear Transition Metal Clusters under Hydrothermal Conditions. 3. Structure and Characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}·4H2O

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posted on 28.05.2007, 00:00 by Shou-Tian Zheng, Da-Qiang Yuan, Jie Zhang, Guo-Yu Yang
A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}·4H2O (1, enMe = 1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P1̄; a = 12.5105(2), b = 14.3710(2), c = 17.2687(2) Å; α = 98.834(1), β = 110.744(1), γ = 104.711(1)°; V = 2704.57(7) Å3; ρ = 3.646 g/cm3; Z = 1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions:  Six of them form an unprecedented inorganic−organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu−OW bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.

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