Carboxylate Ligand‐supported Ag_n (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

Abstract

Structural transformation is important for the study of silver cluster compounds, in which controlled synthesis of their shapes and sizes via anion template-driven is one key scientific question. In this work, the CO 3 2À anion templates were captured by the [ t BuC�CAg] n system under the stimulation induced by carboxylate ligand CF 3 COO À /PhCOO À , and two silver alkynyl clusters [(CO 3 2À )@Ag 21 ( t BuC�C) 16 (CF 3 COO) 3 (H 2 O)]•DMF•2CH 2 Cl 2 (1) and [(CO 3 2À ) 2 @Ag 24 ( t BuC�C) 16 (PhCOO) 4 ]•CH 3 OH•4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO 3 2Àtemplates from single to double, the outer silver atoms from twenty-one to twenty-four, accompanied by the growth of the cluster skeleton from 9.8 Å × 6.9 Å of the (CO 3 2À )@Ag 21 unit to 10.5 Å × 7.3 Å of the (CO 3 2À ) 2 @Ag 24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.