用于多相催化氧化脱硫和叠氮化物-炔烃“点击”反应的多金属氧酸盐桥连的Cu(I)和Ag(I)硫代杯[4]芳烃二聚体
Polyoxometalate-Bridged Cu(I)- and Ag(I)-Thiacalix[4]arene Dimers for Heterogeneous Catalytic Oxidative Desulfurization and Azide-Alkyne "Click" Reaction.
作者信息
Yu Ming-Yue, Guo Ting-Ting, Shi Xiao-Chuan, Yang Jin, Xu Xianxiu, Ma Jian-Fang, Yu Zhen-Tao
机构信息
Key Lab for Polyoxometalate Science, Department of Chemistry , Northeast Normal University , Changchun 130024 , People's Republic of China.
College of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of Education , Shandong Normal University , Jinan 250014 , People's Republic of China.
出版信息
Inorg Chem. 2019 Aug 19;58(16):11010-11019. doi: 10.1021/acs.inorgchem.9b01557. Epub 2019 Aug 6.
Two remarkable polyoxometalate-bridged Cu(I)- and Ag(I)-thiacalix[4]arene dimers, namely, [Cu(SiWO)(L)(DMF)]·2EtOH·DMF () and [Ag(PMoO)(L)]·OH (), were prepared by using a new thiacalix[4]arene, metal cation and polyoxometalate (L = tetra[2-(ethylthio)-1-methyl-1-imidazole]-thiacalix[4]arene). In and , two thiacalix[4]arenes were linked together by one [SiWO] or [PMoO] anion via two metal cations to give a molecular dimer. Further, adjacent dimers were extended into a high-dimensional supramolecular architecture through hydrogen bonds. Markedly, these molecular dimers are exceedingly stable in organic solvents and then were employed as efficient catalysts for catalytic oxidation desulfurization as well as the azide-alkyne "click" reaction.
通过使用一种新型的硫杂杯[4]芳烃、金属阳离子和多金属氧酸盐（L = 四[2-(乙硫基)-1-甲基-1-咪唑基]-硫杂杯[4]芳烃），制备了两种引人注目的多金属氧酸盐桥联的Cu(I)-和Ag(I)-硫杂杯[4]芳烃二聚体，即[Cu(SiWO)(L)(DMF)]·2EtOH·DMF ( ) 和 [Ag(PMoO)(L)]·OH ( )。在 和 中，两个硫杂杯[4]芳烃通过一个[SiWO]或[PMoO]阴离子经由两个金属阳离子连接在一起，形成一个分子二聚体。此外，相邻的二聚体通过氢键扩展成一个高维超分子结构。值得注意的是，这些分子二聚体在有机溶剂中极其稳定，随后被用作催化氧化脱硫以及叠氮化物-炔烃“点击”反应的高效催化剂。
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