Coinage metal clusters: From superatom chemistry to genetic materials

[Display omitted] •A summary of structural evolution and gas-phase reactivity of coinage metal clusters.•Advances in metal nanoclusters (NCs) with emphasis on catalysis and photochemistry.•The correlation between the NCs and corresponding naked metal clusters is emphasized. Building metal materials with well-defined components and the monomer-genetic property is one of the foremost challenges in chemistry and materials science. In recent years, metal nanoclusters especially those of coinage groups (i.e., Cu, Ag, and Au) have received reasonable research interest due to the availability of atomic-level precision via joint experimental and theoretical methods, enabling to unveil the mechanisms in diverse nano-catalysts and functional materials. A variety of ligand-protected metal nanoclusters (NCs) and solid-supported metal clusters have found high catalytic activity and unique selectivity in many catalytic reactions, shedding light on the size effect and active-sites mechanism, providing rational and quantitative information of surface charge state and metal-support interactions. Some ligand-protected metal NCs have been illustrated to exhibit superatom characteristics of the metallic core. This review aims to fully unveil the chemistry of coinage metal clusters. To begin with structural evolution and reactivity, we introduce the catalysis and photochemistry of coinage metal clusters from the point of view of charge-transfer redox and frontier orbitals, and bring forth a proposal to establish superatom chemistry and to connect cluster science and new materials of “cluster genes” as named cluster-genetic materials.