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.