Carboxylate Ligand-supported Ag_n (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 Å ×6.9 Å of the (CO₃ ^2- )@Ag₂₁ unit to 10.5 Å ×7.3 Å of 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.