Mercaptan Ligand Effect in Determining the Geometric Structures of Silver Nanoclusters

The exploitation of the ligand effect in directing the geometric/electronic structures of metal nanoclusters is of great significance in investigating their structure-property correlations at the atomic level. We herein successfully synthesized and structurally determined two structure-correlated silver nanoclusters, Ag₆(SPh^pF)₅(DPPF)₃ and Ag₇(SPhCl₂)₇(DPPF)₂ (DPPF = 1,1’-bis(diphenylphosphino)ferrocene). Because of the mercaptan ligand effect, the geometric structure of Ag₇(SPhCl₂)₇(DPPF)₂ was similar to Ag₆(SPh^pF)₅(DPPF)₃ except that one Ag₁(SR)₂ motif in the former cluster was replaced by a bidentate DPPF ligand. The two silver nanoclusters displayed comparable optical absorptions, suggesting that the ligand effect influenced their electronic structures. Collectively, the research findings in this work introduce the mercaptan ligand effect in directing the structures of silver nanoclusters with low nuclearity.