Abstract
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 [Au25SR18]− nanoclusters adds an excess thiolate ligand and generates a new species, [Au25SR19]0. The addition reaction can be reversed by CO reduction of [Au25SR19]0, leading back to [Au25SR18]− and eliminating precisely one surface ligand. Intriguingly, we show that the ligand shell of Au25 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.
Highlights
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
Tailoring of surface ligands is important considering the total synthesis of metal nanoclusters[6]
Note that purification was needed before electrospray ionization mass spectrometry (ESI-MS) tests, during which the partial oxidation of [Au25(MHA)18]− already took place
Summary
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. We demonstrated the reversible conversion between water-soluble [Au25SR18]− and [Au25SR19]0 nanoclusters with identical thiolate ligand through an oxidative etching/ [Au25SR18]+ nanoclusters reacted with an excess thiolate ligand to form a new isoelectric species, [Au25SR19]0 (N* = 6), O2
Sign-in/Register to view highlights & summary 
Published Version (
Free)
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call