Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand-protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic-inorganic interface (e.g., helical stripes), and the kernel. Herein, a unified picture of metal-ligand surface bonding-induced chirality for the nanoclusters is proposed. The different bonding modes of M-X (where M = metal and X = the binding atom of ligand) lead to different surface structures on nanoclusters, which in turn give rise to various characteristic features of chirality. A comparison of Au-thiolate NCs with Au-phosphine ones further reveals the important roles of surface bonding. Compared to the Au-thiolate NCs, the Ag/Cu/Cd-thiolate systems exhibit different coordination modes between the metal and the thiolate. Other than thiolate and phosphine ligands, alkynyls are also briefly discussed. Several methods of obtaining chiroptically active nanoclusters are introduced, such as enantioseparation by high-performance liquid chromatography and enantioselective synthesis. Future perspectives on chiral NCs are also proposed.