Single-gold etching at the hypercarbon atom of C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes

Chemical etching of nano-sized metal clusters at the atomic level has a high potential for creating metal number-specific structures and functions that are difficult to achieve with bottom-up synthesis methods. In particular, precisely etching metal atoms one by one from nonmetallic element-centred metal clusters and elucidating the relationship between their well-defined structures, and chemical and physical properties will facilitate future materials design for metal clusters. Here we report the single-gold etching at a hypercarbon centre in gold(I) clusters. Specifically, C -centred hexagold(I) clusters protected by chiral N -heterocyclic carbenes are etched with bisphosphine to yield C -centred pentagold(I) ( CAu I 5 ) clusters. The CAu I 5 clusters exhibit an unusually large bathochromic shift in luminescence, which is reproduced theoretically. The etching mechanism is experimentally and theoretically suggested to be a tandem dissociation-association-elimination pathway. Furthermore, the vacant site of the central carbon of the CAu I 5 cluster can accommodate AuCl, allowing for post-functionalisation of the C -centred gold(I) clusters. The control of atomically precise etching of nano-sized metal clusters is important for understanding their structure-specific properties. Here, the authors report the etching of a single gold atom on a hypercarbon centre of gold(I) clusters.