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Three inorganic-organic hybrid complexes, [Cu(Hbiim)(OH)](SiWO)·2HO ( 1), [Cu(Hbiim)](SiWO)·2HO ( 2) and [Ag(Hbiim)](SiWO)·2HO ( 3) (Hbiim = 2, 2′-biimidazole), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, PXRD, TG and single-crystal X-ray diffraction. The crystallographic analysis reveals that in compounds 1- 3, the Keggin polyanions [ α-SiWO] act as inorganic building blocks, which are linked with the dinuclear metal-organic units via Cu-O bonds in compound 1, or through supramolecular interactions in compounds 2 and 3. Compound 1 shows a 3D supramolecular structure constructed by net-like layers. Compounds 2 and 3 display 2D layer structures which were composed of wave-like chains. In addition, these compounds show electrochemical activities, and photoluminescence properties are measured in the solid state. [ABSTRACT FROM AUTHOR]

Abstract: Two new compounds based on Weakley-sandwich-type polyanion (WSP), H2[Mn(en)2]2[Mn(en)2(H2O)]2[Mn4(H2O)2(PW9O34)2]·9H2O (1) and Na2[Co(en)2]2[{Co(en)2(H2O)]2[Co4(H2O)2(PW9O34)2]·9H2O (2) (en=ethylenediamine), have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [a-A-PW9O34]9− with transition metal ions and en, and structurally characterized by routine physical methods and single-crystal X-ray diffraction. Compound 1 represents a 1D chain structure made up of WSPs and [Mn(en)2]2+ ions. Compound 2 represents a 2D layer structure formed by the interconnection of WSPs, [Co(en)2]2+ and Na+ ions. Compounds 1 and 2 represent the first example of high-dimensional construction based on WSPs and transition metal complexes (TMCs), in which the water molecules located on the featured tetra-metal unit are still remained, and exhibit the property of sorption/desorption of water molecules. [Copyright &y& Elsevier]