Control of single-ligand chemistry on thiolated Au25 nanoclusters

Yitao Cao, Victor Fung, Qiaofeng Yao, Tiankai Chen, Shuangquan Zang, Jiang De-en () and Jianping Xie ()
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Yitao Cao: National University of Singapore
Victor Fung: University of California
Qiaofeng Yao: National University of Singapore
Tiankai Chen: National University of Singapore
Shuangquan Zang: Zhengzhou University
Jiang De-en: University of California
Jianping Xie: National University of Singapore

Nature Communications, 2020, vol. 11, issue 1, 1-7

Abstract: 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.

Date: 2020
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DOI: 10.1038/s41467-020-19327-2

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