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 S^2- 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.