Anion-templated silver thiolated clusters effected by carboxylate ligands
Yu-Han Xia, Xin-Yan Xia, Jun-Jie Fang, Zheng Liu, Yun-Peng Xie*, and Xing Lu
Dalton Trans., 2022. https://doi.org/10.1039/D2DT02194C
Abstract：Under the guidance of anion templates V10O286- and SO42-, the novelty of assembly can be increased by using different carboxylate ligands. Herein, the synthesis, crystal structure and electrochemical properties of three anion-templated silver thiolated clusters are reported, namely V10O28@Ag46(iPrS)28(CF3CO2)12(DMF)2 (1), V10O28@Ag46(iPrS)30(CF3CO2)8(PhCO2)2(DMF)4 (2), [SO4@Ag20(iPrS)10(PTA)3(HPTA)2]n (3, H2PTA = phthalic acid). Single-crystal X-ray diffraction analysis showed that 1 and 2 are discrete clusters V10O28@Ag46. Additional PhCO2H was added in the second step of 1 to obtain 2 with different organic shells. If the additional addition is H2PTA, 3 of the three-dimensional (3D) structure containing the SO42- template can be obtained. Both V10O286- and SO42- templates were generated in situ under solvothermal conditions. This work is the first to obtain the heterogeneous silver clusters containing V10O286- anion template protected by isopropyl thiolate ligand and Ag20 cluster with 3D structure. The assembly process influenced by carboxylic acid deserves continuous exploration in the future.
摘要：在阴离子模板V10O286-和SO42-的引导下，使用不同的羧酸配体可以增加组装的新颖性。本文报道了三种阴离子模板化硫银簇的合成、晶体结构和电化学性质，即V10O28@Ag46(iPrS)28(CF3CO2)12(DMF)2 (1), V10O28@Ag46(iPrS)30(CF3CO2)8(PhCO2)2(DMF)4 (2), [SO4@Ag20(iPrS)10(PTA)3(HPTA)2]n (3，H2PTA=邻苯二甲酸）。单晶X射线衍射分析表明，1和2是离散的团簇V10O28@Ag46。在1的第二步反应中额外加入PhCO2H，可以得到有机壳层不同的2。如果额外添加的是H2PTA，则可以得到含SO42-模板的三维结构3。V10O286-和SO42-模板都是在溶剂热条件下原位生成的。这项工作首次得到由异丙基硫醇配体保护的含V10O286-阴离子模板的银簇和3D结构的Ag20，由羧酸影响的组装过程值得未来的不断探究。
