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 Au13core of [Au13(NHC)8Br4]+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. © 2022 American Chemical Society. All rights reserved.