具有天线分子的3D过渡金属单取代Keggin型多金属氧酸盐：合成、结构与表征

3D-transition metal mono-substituted Keggin polyoxotungstate with an antenna molecule: synthesis, structure and characterization.

作者信息

Liu Hongsheng, Gómez-García Carlos J, Peng Jun, Sha Jingquan, Li Yangguang, Yan Yechao

机构信息

Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, P. R. China.

出版信息

Dalton Trans. 2008 Nov 28(44):6211-8. doi: 10.1039/b805714a. Epub 2008 Sep 25.

DOI:10.1039/b805714a

PMID:18985254

Abstract

Three new organic-inorganic hybrid complexes based on 3d-transition metal monosubstituted Keggin polyoxometalates (POMs) with imidazole (Im) as pendant ligands, formulated as (HIm)(6-)[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2.7H2O (1), (Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31.7.5H2O (2) and (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37.7H2O (3), have been synthesized and characterized by IR spectroscopy, UV-visible spectroscopy, elemental analysis, TG analysis, cyclic voltammetry, magnetic properties, EPR and single-crystal/powder X-ray diffraction. The structural analyses indicate that the 3d metal atoms are incorporated into the vacancy of the alpha-SiW11O39 (SiW11). Complexes 1-3 are the first examples of crystallographically characterized 3d-transition metal mono-substituted POMs with an antenna organic ligand synthesized under normal bench conditions.

摘要

三种基于3d过渡金属单取代的Keggin多金属氧酸盐（POMs）并以咪唑（Im）作为侧基配体的新型有机-无机杂化配合物，其化学式分别为(HIm)(6-)[SiW11O39NiIm]0.8[SiW11O39Ni(H2O)]0.2·7H2O (1)、(Im)4Na6[SiW11O39MnIm]0.69[SiW11O39Mn(H2O)]0.31·7.5H2O (2) 和 (HIm)6[SiW11O39CoIm]0.63[SiW11O39Co(H2O)]0.37·7H2O (3)，已通过红外光谱、紫外可见光谱、元素分析、热重分析、循环伏安法、磁性、电子顺磁共振以及单晶/粉末X射线衍射进行了合成与表征。结构分析表明，3d金属原子被引入到α-SiW11O39（SiW11）的空位中。配合物1 - 3是在常规实验室条件下合成的具有晶体学表征的带有天线有机配体的3d过渡金属单取代POMs的首个实例。