New self-assembly hybrid compounds based on arsenic-vanadium clusters and transition metal mixed-organic-ligand complexes

Seven novel compounds based on arsenic-vanadium clusters [Ni(im)(2,2'-bpy)](2)[Ni(im)(2)](2)[Ni(2,2'bpy)][As8V14O42(H2O)] (1), [Ni(2,2'-bpy) 3][Ni(im)(2)](0.5)[Ni(2,2'-bpy)(im)][As8V14O42(H2O)] (1a), [Ni(2,2'bpy)(phen)][Ni(2,2'-bpy)(2)][As8V14O42(H2O)]center dot H2O (2) and [Ni(2,2'-biim)(2,2'-bpy)(2)](2)[As8V14O42(H2O)]center dot 6H(2)O (3), [Cd(2,2'-bpy)(phen)(2)](2)[As8V14O42(H2O)]center dot 4H(2)O (4), [Cd-4(phen)4(ox)(H2O)(6)][As6V15O42(H2O)]center dot 2H(2)O (5) and [Co-2(phen)(4)(ox)](H2As8V14O42(H2O)]center dot(apy)(2)center dot 2H(2)O (6) (Him = imidazole, phen = 1,10-phenanthroline, 2,2'biim = 2,2'-biimidazole, apy = 2-aminopyridine) have been synthesized and characterized by IR, UV-vis, XRD, TG, CD spectrum, elemental analysis and single-crystal X-ray diffraction analysis. Crystal analysis reveals that compound 1 is the first example of a hybrid compound constructed from polyoxometalates and transition metal mixed-organic-ligand complexes of negatively charged nitrogen-containing ligands and neutral nitrogen-containing ligands. Compound 1a is the first example of a POM supported TMC which is formed via arsenic-metal contact. Compound 2 is a chiral compound which exhibits a novel 1-D triple-chain structure constructed from[As8V14O42(H2O)](4-) clusters, a type of chiral transition metal mixed-organic-ligand complex and a type of chiral transition metal complex. Compounds 3 and 4 are supramolecular compounds which are formed by [As8V14O42(H2O)](4-) clusters and transition metal mixedorganic- ligand complexes, respectively. Compounds 5 and 6 are constructed from arsenic-vanadium clusters and transition metal complexes of nitrogen-containing ligands and oxalic groups. The catalytic properties of compounds 1 and 2-6 have been investigated and we found that the transition metal mixed-organic-ligand complexes have dramatic influences on the catalytic properties of catalysts.