Control of single-ligand chemistry on thiolated Au25 nanoclusters

Cao, Yitao; Fung, Victor; Yao, Qiaofeng; Chen, Tiankai; Zang, Shuangquan; Jiang, De-en; Xie, Jianping

doi:10.1038/s41467-020-19327-2

Control of single-ligand chemistry on thiolated Au₂₅ nanoclusters

Journal Article · Fri Oct 30 00:00:00 EDT 2020 · Nature Communications

DOI:https://doi.org/10.1038/s41467-020-19327-2· OSTI ID:1817097

Cao, Yitao ^[1]; ^[2]; ^[1]; Chen, Tiankai ^[1]; ^[3]; ^[2]; ^[4]

National Univ. of Singapore (Singapore)
Univ. of California, Riverside, CA (United States)
Zhengzhou University (China)
National Univ. of Singapore (Singapore); Joint School of National University of Singapore and Tianjin University (China)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Ministry of Education, Singapore

OSTI ID:: 1817097

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 11; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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