Department of Chemistry, Emory University, Atlanta, GA 30322, USA.
Dalton Trans. 2012 Sep 7;41(33):9908-13. doi: 10.1039/c2dt30733b. Epub 2012 Jul 23.
A dodecazinc silicotungstate K(20)Na(2)Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))·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) frameworks make this complex more stable hydrolytically than the heteropolytungstate ligands, Si(2)W(18)O(66), themselves. The structurally unique central Zn(12) core is formed by the fusion of two Zn(6)(OH)(7)(H(2)O) 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.
一种十二锌硅钨酸盐 K(20)Na(2)Zn(6)(OH)(7)(H(2)O)(Si(2)W(18)O(66))·34H(2)O（1）已通过 X 射线晶体学、元素分析、红外、紫外-可见光谱、循环伏安法、酸碱滴定和 DFT 计算进行了合成和表征。两个 Si(2)W(18)O(66) 框架之间的十二个锌原子使该配合物在水解方面比杂多钨酸盐配体 Si(2)W(18)O(66) 本身更稳定。结构独特的中心 Zn(12)核由两个通过两个边缘共享 Zn6 原子融合的 Zn(6)(OH)(7)(H(2)O) 单元形成。DFT B3LYP 计算给出的 HOMO-LUMO 和 (HOMO - 1)-LUMO 能隙分别约为 3.65 和 3.91 eV，而 ZnO 的能带隙为 3.35 eV。
