Ligand-Induced Modulation of Photoluminescence in Atomically Precise Silver Nanoclusters

Ligand engineering has emerged as an impressive strategy for modulating the optical properties of atomically precise nanoclusters that exhibit molecule-like behavior. Establishing systematic correlations between well-defined structures and their corresponding properties remains a critical challenge in this field. In this study, we compare the crystal structures and photoluminescence characteristics of a pair of alkyne-functionalized Ag₃ nanoclusters differentiated by their electronic and steric factors. The clusters bearing aromatic alkyne ligands exhibit predominantly ligand-centered emission, whereas those stabilized by aliphatic alkyne ligands display metal-centered emission. Based on these observations, we elucidate the distinct origins of photoluminescence by correlating structural distortions with the resulting photoluminescence properties.