Control of single-ligand chemistry on thiolated Au nanoclusters.

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [AuSR] nanoclusters adds an excess thiolate ligand and generates a new species, [AuSR]. The addition reaction can be reversed by CO reduction of [AuSR], leading back to [AuSR] and eliminating precisely one surface ligand. Intriguingly, we show that the ligand shell of Au nanoclusters becomes more fragile and rigid after ligand addition. This reversible addition/elimination reaction of a single surface ligand on gold nanoclusters shows potential to precisely control the number of surface ligands and to explore new ligand space at each nuclearity.