Assembly of organic-inorganic hybrid supramolecular materials based on {P2W18O62}6- anion and Cu(II)/Mn(II) complex

Six novel hybrids based on Wells-Dawson polyoxometalates, [{Cu-0.5(imi)(O0.5H)Cu-0.5(imi)(2)}(2){Cu-0.5(imi)}(2)(P2W18O62)]center dot 5H(2)O (1), (Himi)(2)[{Mn(2,2'-bpy)(2)}(2)(P2W18O62)]center dot H2O (2), (Himi)(2)[{Cu(2,2'-bpy)(2)}(2) (P2W18O62)]center dot H2O (3), [Cu(phen)(2)Cl](2)[{Cu(phen)(H2O)(gly)Cu(phen)}(P2W18O62)]center dot 3H(2)O (4) [Mn(phen)(3)][{Mn(phen)(2)(H2O)}(2)(P2W18O62)]center dot 3.5H(2)O (5), and (H(2)phen)[Mn(phen)(3)][{Mn(phen)(H2O)(3)}(P2W18O62)]center dot 3.5H(2)O (6), (imi = imidazole, bpy = bipyridine, phen = 1,10-phenanthroline, gly = glycine), have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, UV, TG, and single-crystal X-ray diffraction. Compound 1 represents an unprecedented 2D metal-organic layer based on hexad-supported {P2W18O62}(6-) (abbreviated to P2W18) anions and Cu-imi complexes linker. Compounds 2 and 3 exhibit similar 1-D chains. Compound 4 displays a 1-D chain built by {P2W18} clusters and an unusual binuclear complex {Cu(phen)(H2O)(gly)Cu(phen)} linker. Compounds 5 and 6 are bi-supported and mono-supported 0-D clusters. All the clusters are further packed into various 3-D assemblies via strong hydrogen-bonding and supramolecular interactions. Furthermore, electrochemical behavior and magnetic properties of 1-6 have been investigated in detail.