Hydrothermal syntheses, crystal structures of three new organic–inorganic hybrids constructed from Keggin-type [BW12O40]5− clusters and transition metal complexes

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.