Structurally Precise Dichalcogenolate-Protected Copper and Silver Superatomic Nanoclusters and Their Alloys

ConspectusThe chalcogenolato silver and copper superatoms are currently a topic of cutting edge research besides the extensively studied Aun(SR)m clusters. Crystal structure analysis is an indispensable tool to gain deep insights into the anatomy of these sub-nanometer clusters. The metal framework and spatial arrangement of the chalcogenolates around the metal core assist in unravelling the structure–property relationships and fundamental mechanisms involved in their fabrication. In this Account, we discuss our contribution toward the development of dichalcogenolato Ag and Cu cluster chemistry covering their fabrication and precise molecular structures. Briefly introducing the significance of the single crystal structures of the atomically precise clusters, the novel dichalcogenolated two-electron superatomic copper and its alloy systems are presented first. The [Cu13{S2CNR}6{C≡CR′}4]+ is so far the first unique copper cluster having Cu13 centered cuboctahedra, which is a miniature of bulk fcc structure....