Polyoxometalate Modified Chemical

In this paper, six novel molybdenum phosphates, [H3N(CH2)4NH3]-(H3O)2[{Mn(phen)2}4{MnMov,2O30(HPO4)6(H2PO4)2}]-4H2O1, Na2[{Mn-(phen)2(H2O)} {Mn(phen)2}3{MnMov12O24(HPO4)6(PO4)2(OH)6}]-4H2O 2,[Co4(phen)8(H2O)2(HPO3)2](H3O)3[PMoVI8VIV4O40(VIVO)2] 3, [PMovI6-Mov2VIV8O44 {Co(2,2' -bipy)2(H2O) } 4] [PMoVI4Mov4VIV8O44 {Co(2,2'-bipy) 2(H2O)}2]-4H2O 4, [CuI(phen)2]4[PMovl8VIV6O42(Cul(phen)}2]-H5O2 5 and [Ni(phen)3][PMovl9Mov3O40{Ni(phen)}2] 6 (2,2'-bipy = 2,2'-bipyridine, phen = 1.10-phenanthroline), have been hydrothermally synthesized and characterized by IR, UV, EPR, XPS, TGA and single-crystal X-ray diffraction. Compound 1 and 2 are both built on {Mn(Mo6P4)2} dimers linked through {Mn(phen)2} complexes into extended frameworks. The introduction of the second organoamine causes the difference between the structures of compound 1 and 2: compound 1 exhibits a 1D chain with rectangular cavities, while compound 2 exhibits a 2D framework with two new types of tunnels formed in its solid. Compound 3 successfully combines inorganic-organic hybrid transition metal phosphites with a highly reduced capped polyoxometalates through hydrogen-bonding interactions to obtain a new type of 2D supramolecular composite solid-state material. Noteworthily, in the structure of 4, heteropoly-oxocations and heteropolyoxoanions are coexistly involved in the same crystal due to the modifying effect of transition metal complexes; compound 6 unprecedentedly incorporates divalent transition metal into the heteropolyanion cluster as capping atoms and provides a new mode of supporting transition metal complexes as well.