Robust Enantiomeric Two-Dimensional Assembly of Atomically Precise Silver Clusters

The facile syntheses of enantiomeric atomically precise silver clusters starting from achiral ligands remain a substantial challenge to explore. In this work, a pair of atomically precise enantiomers of R/S-[Ag17Cl(iPrS)9S(CH3COO)5H2O] (R/S-Ag17, iPrS = isopropanethiolate) clusters have been synthesized using a viable solvothermal approach. The chirality of the resulting enantiomeric R/S-Ag17 clusters is attributed to the asymmetric arrangement of surface achiral ligands. Both R/S-Ag17 enantiomers could form the two-dimensional (2D) assemblies via intercluster interactions of basic building blocks containing Ag16S8 moieties, iPrS-Ag motifs, and S2- linkers. Such a small ligand-induced 2D assembly greatly contributes to the enhancement of thermal stability and photocatalytic activity of R/S-Ag17 clusters, providing possibilities for exploring robust coinage cluster-based assembly with attractive catalytic properties.