Ag₄₈ and Ag₅₀ Nanoclusters: Toward Active-Site Tailoring of Nanocluster Surface Structures

The determination of active sites in metal nanoclusters is of great significance for the in-depth understanding of the structural evolution and the mechanism of physicochemical properties. In this work, the surface active Ag₂(SR)₃ units of the Ag₄₈Cl₁₄(S-Adm)₃₀ nanocluster are determined, and the active-site tailoring of this nanocluster gives rise to two derivative nanoclusters, i.e., the structure-maintained Ag₄₈Cl₁₄(S-Adm)₂₆(S-c-C₆H₁₁)₄ and the structure-growth Ag₅₀Cl₁₆(S-Adm)₂₈(DPPP)₂. Both Ag₄₈ and Ag₅₀ nanoclusters exhibit almost the same cluster framework, but the Ag₂(S-Adm)₃ active units are regulated to Ag₃(S-Adm)₂(DPPP)₁Cl₁ with the transformation from Ag₄₈ to Ag₅₀. The surface active sites on Ag₄₈ are rationalized by analyzing its crystal structure and the ligand-exchange-induced cluster transformation. This study provides some inspiration toward the active-site tailoring of nanocluster surface structures, which is significant for the preparation of new cluster-based nanomaterials with customized structures and enhanced performance.