Controlled Triol-Derivative Bonding and Decoration Transformation on Cu-Centered Anderson–Evans Polyoxometalates

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• 作者：Yang Wang ; Bao Li ; Hujun Qian ; Lixin Wu
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4271-4277
• 全文大小：388K
• 年卷期：0
• ISSN：1520-510X

文摘

To create new types of organic ligands covalently grafted onto polyoxometalates and identify the reaction mechanism, we selected Cu^II as the central heteroatom for the synthesis of a series of disklike Anderson–Evans clusters bearing different triol derivatives on both their faces via one-pot and/or step-by-step routes. By using a [(n-C₄H₉)₄N]₄[Mo₈O₂₆] precursor cluster and copper acetate as the starting materials, several organically modified χ isomers with Cu^II heteroatom centers were obtained. Starting from a [(n-C₄H₉)₄N]₂[Mo₂O₇] subcluster, however, a half-malposition coordination fashion of triol ligands with a δ isomer on one face and a χ isomer on the other face of the Anderson–Evans cluster was obtained. By changing the reaction solvent from acetonitrile to methanol, we realized a secondary organic modification of the triol-grafted clusters and obtained a triol ligand/methanol codecoration on the Anderson–Evans polyoxometalate. In addition, by changing the reaction environment, we succeeded in modulating the transformation of triol ligands from one site to another on the polyoxometalate cluster. Importantly, by control of the reaction condition, the methanol molecules were also taken off from the cluster.