LAUSR

Under the guidance of anion templates V10O286- and SO42-, the novelty of cluster 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), and [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. The addition of PhCO2H in the second step of 1 leads to obtaining 2 with different organic shells. If the addition of H2PTA is made, 3 with a 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 where heterogeneous silver clusters containing the V10O286- anion template protected by an isopropyl thiolate ligand and a Ag20 cluster with a 3D structure are obtained. The assembly process influenced by carboxylic acid deserves to be continuously explored in the future.