Ligand-Induced Cuboctahedral versus Icosahedral Core Isomerism within Eight-Electron Heterocyclic-Carbene-Protected Gold Nanoclusters.

The controlled structural modification of ligand-protected gold clusters is evaluated by a proper variation of the size and shape of N-heterocyclic carbene (NHC) ligands. Density functional theory calculations show that the Au core of [Au(NHC)Br] can be shaped into an icosahedron and/or a so far unexpected cuboctahedron depending on the sterical effect inferred by the NHC ligand side arms. As a result, the cluster properties can be modified, encouraging further exploration on controlled core isomerization in ligated gold cluster chemistry.