| 3 On the basis of molecular design and assembly, the bi-, tetra- and hexa-nuclear sandwich-type compounds based on Keggin trivacant heteropolyanions and a 1D fourfold complex based on saturated Keggin anions were successfully synthesized by routine methods or hydrothermal reactions, and characterized by X-ray crystallography, spectroscopic, thermal and electrochemical.(1) Using hydrothermal synthetic technology, we have synthesized two hexanuclear copper(II) substituted tungstogermanates [Cu(2,2'-bipy)]2[Cu(2,2'-bipy)2]2[Cu6(2, 2'-bipy)2(GeW9O34)2]·3H2O (1) and (Cuphen)2[Cu(phen)2]2[Cu6phen2(GeW9O34) 2]·2H2 O (2). They represent unreported two examples of Cu6-containing tungstog- ermanates and further act as netural molecular units for the construction of interesting three-dimensional supramolecular frameworks.(2) Under routine conditions, we have synthesized three symmetrical sandwich type compounds, Na10H2[Cu2(GeMo9O33)2]·41H2O (3) Na5.5H0.5[(CH3)4N]4[Cr2(GeMo9 O33)2]·27.5H2O (4) Na11H[Ni4(H2O)2(GeMo9O34)2]·30H2O (5). Compounds 3 and 4 display symmetrical sandwich-type polyanion frameworks based on trivicant building unit [B-α-GeMo9O33]8-, while Compound 5 display sandwich-type polyanion framework based on [B-GeMo9O34]10-.(3) We obtained an organic-inorganic hybrid based on saturated Keggin polyanion [SiW12O40]4-: [Cu(4,4'-bipy)]2[SiW12O40{Cu(4,4'-bipy)}4]·(OH)2·H2O (6), which display a 1D fourfold chain by the connections of Cu-Ot.The compounds were characterized by IR, UV spectroscopy, single crystal X-ray structural analysis, and studied by TG, electrochemical.
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