Atom-Precise Modification of Silver(I) Thiolate Cluster by Shell Ligand Substitution: A New Approach to Generation of Cluster Functionality and Chirality.

To realize the molecular design of new functional silver(I) clusters, a new synthetic approach has been proposed, by which the weakly coordinating ligands NO3- in a Ag20 thiolate cluster precursor can be substituted by carboxylic ligands while keeping its inner core intact. By rational design, novel atom-precise carboxylic or amino acid protected 20-core Ag(I)-thiolate clusters have been demonstrated for the first time. The fluorescence and electrochemical activity of the postmodified Ag20 clusters can be modulated by alrestatin or ferrocenecarboxylic acid substitution. More strikingly, when chiral amino acids were used as postmodified ligands, CD-activity was observed for the Ag20 clusters, unveiling an efficient way to obtain atom-precise chiral silver(I) clusters.