Anion-templated silver thiolated clusters affected by carboxylate ligands.

Under the guidance of anion templates V 10 O 28 6- and SO 4 2- , 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 V 10 O 28 @Ag 46 ( i PrS) 28 (CF 3 CO 2 ) 12 (DMF) 2 (1), V 10 O 28 @Ag 46 ( i PrS) 30 (CF 3 CO 2 ) 8 (PhCO 2 ) 2 (DMF) 4 (2), and [SO 4 @Ag 20 ( i PrS) 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 V 10 O 28 @Ag 46 . The addition of PhCO 2 H 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 SO 4 2- template can be obtained. Both V 10 O 28 6- and SO 4 2- templates were generated in situ under solvothermal conditions. This work is the first where heterogeneous silver clusters containing the V 10 O 28 6- 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.