A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands

作者：Zhu Guibo; Geletii Yurii V; Zhao Chongchao; Musaev Djamaladdin G; Song Jie; Hill Craig L^*

来源：Dalton Transactions, 2012, 41(33): 9908-9913.

DOI：10.1039/c2dt30733b

A dodecazinc silicotungstate K20Na2[Zn-6(OH)(7)(H2O)(Si2W18O66)](2)center dot 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 [Si2W18O66](16-) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, [Si2W18O66](16-), themselves. The structurally unique central Zn-12 core is formed by the fusion of two [Zn-6(OH)(7)(H2O)](5+) units through two edge-sharing Zn6 atoms. DFT B3LYP calculations give HOMO-LUMO and (HOMO - 1)-LUMO energy gaps of similar to 3.65 and 3.91 eV, respectively, as compared to the band gap in ZnO of 3.35 eV.

• 出版日期2012