Anion-templated silver thiolated clusters affected by carboxylate ligands

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@Ag-46((PrS)-Pr-i)(28)(CF3CO2)(12)(DMF)(2) (1), V10O28@Ag-46((PrS)-Pr-i)(30)(CF3CO2)(8)(PhCO2)(2)(DMF)(4) (2), and [SO4@Ag-20((PrS)-Pr-i)(10)(PTA)(3)(HPTA)(2)](n) (3, H(2)PTA = phthalic acid). Single-crystal X-ray diffraction analysis showed that 1 and 2 are discrete clusters V10O28@Ag-46. The addition of PhCO2H in the second step of 1 leads to obtaining 2 with different organic shells. If the addition of H(2)PTA 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 Ag-20 cluster with a 3D structure are obtained. The assembly process influenced by carboxylic acid deserves to be continuously explored in the future.

Automated summary

Under the guidance of anion templates V10O286- and SO42-, the novelty of cluster assembly can be increased by using different carboxylate ligands. In this work, three anion-templated silver thiolated clusters were synthesized and characterized. The results showed that the addition of different organic shells and the use of different templates can lead to the formation of discrete clusters or clusters with a three-dimensional structure. This study provides important insights into the assembly process and the potential applications of these silver clusters.