Carboxylate Ligand-supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions.

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 CO3 2- anion templates were captured by the [t BuC≡CAg]n system under the stimulation induced by carboxylate ligand CF3 COO- /PhCOO- , and two silver alkynyl clusters [(CO3 2- )@Ag21 (t BuC≡C)16 (CF3 COO)3 (H2 O)]⋅DMF⋅2CH2 Cl2 (1) and [(CO3 2- )2 @Ag24 (t BuC≡C)16 (PhCOO)4 ]⋅CH3 OH⋅4DMF (2) have been successfully isolated and charactered. With the increase of the number of CO3 2- templates 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 Š×6.9 Šof the (CO3 2- )@Ag21 unit to 10.5 Š×7.3 Šof the (CO3 2- )2 @Ag24 unit. In addition, the syntheses, structures, photocurrent responses, cyclic voltammetry characteristics, luminescence, and photodegradation of compounds 1 and 2 have been studied.