Insight into the Stability and Electronic and Optical Properties of N-Heterocyclic Carbene Analogues of Halogen/Phosphine-Protected Au13Superatomic Clusters

Atomically precise gold nanoclusters (AuNCs) belong to a relevant area offering useful templates with tunable properties toward functional nanostructures. In this work, we explored the feasible incorporation of N-heterocyclic carbenes (NHCs), as part of the protecting-ligand shell in AuNCs. Our results, which are based on the substitution of phosphine ligands in experimentally characterized AuNCs by NHCs in various eight-electron superatoms Au13 and M4Au9 (M = Cu, Ag), indicate similar electronic structure and stability but somewhat different optical properties. These findings support the feasible obtention of novel targets for explorative synthetic efforts featuring NHC ligands on medium-sized species based on the recurrent Au13 icosahedral core. The hypothetical species appear to be interesting templates for building blocks in nanostructured materials with tuned properties, which encourage experimental exploration of ligand versatility in homo- and heterometallic superatomic clusters.