Synthesis And Investigation Of The Copper(Ii)-Substituted Polyoxotungstate Based On Alpha-B-[Biw9o33](9-) Units

The new polyoxotungsto-bismutate, Na-12[Cu-3(2+)(H2O)(3)(BiW9O33)(2)]center dot 47H(2)O (1), has been synthesized by reaction of Na-9[BiW9O33]center dot 14H(2)O and Cu(CH3COO)(2)]center dot H2O. in NaAc/HAc buffer under moderate condition. This polyoxoanion was characterized by elemental and thermo-gravimetric analysis, FT-IR, Raman, UV, Vis, EPR spectroscopy, X-ray diffraction on single crystal and cyclic voltammetry. This allowed for the subsequent determination of the behavior of the encapsulated transition metal ions, their coordination by the tungstobismutate (III) fragments, the corresponding local symmetry and the type of metal-metal interactions. Compound 1 consists of two alpha-B-[BiW9O33](9-) units, which are linked by an equatorial belt of three Cu(H2O)(2+) cations. Three Na(H2O)(2+) cations are also attached to the equatorial plane. The bond geometry is square-pyramidal against each Cu atom and trigonal-prismatic against each Na atom. Crystal data for 1 are: monoclinic, space group C2c, a=14.049(12) angstrom, b=23.360(19) angstrom, c=31.991(3) angstrom, alpha=90 degrees, beta=99.217(2)degrees, gamma=90 degrees, V=10364.2(15) angstrom(3), Z=4.