Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

Abstract Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface‐capping‐agent displacement is challenging. Herein, [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ] ( Ag 14 ‐DMF ; DMF= N , N ‐dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed‐ligands strategy. Owing to the high surface reactivity of Ag 14 ‐DMF , the surface ligands are labile, easily dissociated or exchanged by other ligands. Based on the enhanced surface reactivity, easy modulation of the optical properties of Ag 14 by reversible “on‐off” DMF ligation was realized. When chiral amines were introduced to as‐prepared products, all eight surface ligands were replaced by amines and the racemic Ag 14 clusters were converted to optically pure homochiral Ag 14 clusters as evidenced by circular dichroism (CD) activity and single‐crystal X‐ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.