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Abstract: Three new organic–inorganic hybrid compounds constructed from Keggin-type polyanions and transition metal complexes, [Mn(2,2′-bipy)3]1.5[BW12O40Mn(2,2′-bipy)2(H2O)]·0.25H2O (1), [Fe(2,2′-bipy)3]1.5[BW12O40Fe(2,2′-bipy)2(H2O)]·0.5H2O (2) and [Cu2(phen)2(OH)2]2H[Cu(H2O)2{BW12O40Cu0.75(phen)(H2O)}2]·1.5H2O (3), have been hydrothermally synthesized and characterized by elemental analyses, IR, TGA and single-crystal X-ray diffraction. Compounds 1 and 2 are isostructural and both exhibit monosupporting polyoxometalate cluster structure, each of which contains a [BW12O40]5− cluster decorated by one transition metal complex. Compound 3 contains a bisupporting polyoxometalate cluster anion where two {Cu0.75(phen)(H2O)}0.75+ fragments are supported on the polyoxometalate dimer {Cu(H2O)2(BW12O40)2}8−, this represents the first bisupporting polyoxometalate cluster based on a Keggin-type polyoxometalate dimer, which are further packed together via π–π stacking contacts into an extended 1-D chain. [Copyright &y& Elsevier]

A novel compound, [{Pr(DMSO)6(H2O)}(PMo12O40)·CH3CN]n, has been synthesized and characterized by IR and single crystal X-ray structural analysis. It forms an one-dimensional zigzag chain built from alternating polyanions and cationic units through Mo–Ot–Pr–Ot–Mo links in the crystal. The results of the single crystal X-ray diffraction analyses and IR are agreement and both show the metal cation units are coordinately bonded to the Keggin cluster. The low temperature ESR spectrum indicates thermal electron delocalization occurs among the Mo atoms in the compound. The result of CV shows that the title compound undergoes five two-electron reversible reductions and that [PMo12O40]3− anions are active centre for electrochemical redox in the solutions, while matched cations have small effect on electrochemical redox. [Copyright &y& Elsevier]

A novel compound, [{Gd(NMP)6}(PMo12O40)]n, has been synthesized and characterized by IR, and UV spectroscopy, and single crystal X-ray structural analysis. It forms an unprecedented one-dimensional zigzag chain built from alternating polyanions and cationic units through Mo–Ot–Gd–Ot–Mo links in the crystal. In the compound, Gd3+ is eight-coordinated with a bicapped trigonal prism geometry environment of oxygen atoms. The results of the single crystal X-ray diffraction analyses and IR are agreement and both show the metal cation units are coordinately bonded to the Keggin cluster. The UV spectrum of the title compound suggests that the compound is entirely dissociated in dilute solution. [Copyright &y& Elsevier]