The Pivotal Radical Intermediate [Au₂₁(SR)₁₅]⁺ in the Ligand-Exchange-Induced Size-Reduction of [Au₂₃(SR)₁₆]⁻ to Au₁₆(SR)₁₂

The atomic precision of sub-nanometer-sized metal nanoclusters makes it possible to elucidate the kinetics of metal nanomaterials from the molecular level. Herein, the size reduction of an atomically precise [Au 23 (CHT) 16 ] − (HCHT = cyclohexanethiol) cluster upon ligand exchange with HSAdm (1-adamantanethiol) has been reported. During the 16 h conversion of [Au 23 (CHT) 16 ] − to Au 16 (SR) 12, the neutral 6e Au 21 (SR) 15, and its 1e-reduction state, i.e. the 5e, cationic radical, [Au 21 (SR) 15 ] +, are active intermediates to account for the formation of thermodynamically stable Au 16 products. The combination of spectroscopic monitoring (with UV–vis and ESI-MS) and DFT calculations indicates the preferential size-reduction on the corner Au atoms on the core surface and the terminal Au atoms on longer Au n S n +1 staples. This study provides a reassessment on the electronic state of the Au 21 structure and highlights the single electron transfer processes in cluster systems and thus the importance of the EPR analysis on the mechanistic issues.