Tuning the electronic structure of thiolate-protected 25-atom clusters by co-substitution with metals having different preferential sites

Abstract

Trimetallic Au_24−xAg_xPd and tetrametallic Au_24−x−yAg_xCu_yPd clusters were synthesized by the subsequential metal exchange reactions of dodecanethiolate-protected Au₂₄Pd clusters. EXAFS measurements revealed that Pd, Ag, and Cu dopants preferentially occupy the center and edge sites of the core, and staple sites, respectively. Spectroscopic and theoretical studies demonstrated that the synergistic effects of multiple substitutions on the electronic structures are additive in nature.