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Control of single-ligand chemistry on thiolated Au25 nanoclusters

Author

Listed:
  • 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)

  • De-en Jiang

    (University of California)

  • Jianping Xie

    (National University of Singapore
    Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University Binhai New City)

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.

Suggested Citation

  • Yitao Cao & Victor Fung & Qiaofeng Yao & Tiankai Chen & Shuangquan Zang & De-en Jiang & Jianping Xie, 2020. "Control of single-ligand chemistry on thiolated Au25 nanoclusters," Nature Communications, Nature, vol. 11(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-19327-2
    DOI: 10.1038/s41467-020-19327-2
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    Cited by:

    1. Zhihe Liu & Hua Tan & Bo Li & Zehua Hu & De-en Jiang & Qiaofeng Yao & Lei Wang & Jianping Xie, 2023. "Ligand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    2. Yuan Zhong & Jiangwei Zhang & Tingting Li & Wenwu Xu & Qiaofeng Yao & Min Lu & Xue Bai & Zhennan Wu & Jianping Xie & Yu Zhang, 2023. "Suppression of kernel vibrations by layer-by-layer ligand engineering boosts photoluminescence efficiency of gold nanoclusters," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    3. Claudia Pigliacelli & Angela Acocella & Isabel Díez & Luca Moretti & Valentina Dichiarante & Nicola Demitri & Hua Jiang & Margherita Maiuri & Robin H. A. Ras & Francesca Baldelli Bombelli & Giulio Cer, 2022. "High-resolution crystal structure of a 20 kDa superfluorinated gold nanocluster," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    4. Xiao-Li Pei & Pei Zhao & Hitoshi Ube & Zhen Lei & Masahiro Ehara & Mitsuhiko Shionoya, 2024. "Single-gold etching at the hypercarbon atom of C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    5. Teng Jia & Yi-Xin Li & Xiao-Hong Ma & Miao-Miao Zhang & Xi-Yan Dong & Jie Ai & Shuang-Quan Zang, 2023. "Atomically precise ultrasmall copper cluster for room-temperature highly regioselective dehydrogenative coupling," Nature Communications, Nature, vol. 14(1), pages 1-15, December.

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