title: A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands.
abstract: A dodecazinc silicotungstate K(20)Na(2)[Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))](2)·34H(2)O (1) has been synthesized and characterized by X-ray crystallography, elemental analysis, infrared, UV-vis spectroscopy, cyclic voltammetry, acid-base titration, and DFT calculations. The twelve zinc atoms between the two [Si(2)W(18)O(66)](16-) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, [Si(2)W(18)O(66)](16-), themselves. The structurally unique central Zn(12) core is formed by the fusion of two [Zn(6)(OH)(7)(H(2)O)](5+) units through two edge-sharing Zn6 atoms. DFT B3LYP calculations give HOMO-LUMO and (HOMO - 1)-LUMO energy gaps of ∼3.65 and 3.91 eV, respectively, as compared to the band gap in ZnO of 3.35 eV.
authors: Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
authors: Guibo
authors: G
authors: Zhu
authors: Yurii V
authors: YV
authors: Geletii
authors: Chongchao
authors: C
authors: Zhao
authors: Djamaladdin G
authors: DG
authors: Musaev
authors: Jie
authors: J
authors: Song
authors: Craig L
authors: CL
authors: Hill
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D012825:Silicon / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D012825:Silicon; D017973:Tungsten Compounds; D015032:Zinc; C102296:polyoxometalate I; D000099294:Polyoxometalates