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Single-gold etching at the hypercarbon atom of C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes

Author

Listed:
  • Xiao-Li Pei

    (The University of Tokyo
    Tokyo University of Science)

  • Pei Zhao

    (Myodaiji)

  • Hitoshi Ube

    (The University of Tokyo)

  • Zhen Lei

    (The University of Tokyo
    Fuzhou University)

  • Masahiro Ehara

    (Myodaiji)

  • Mitsuhiko Shionoya

    (The University of Tokyo
    Tokyo University of Science)

Abstract

Chemical etching of nano-sized metal clusters at the atomic level has a high potential for creating metal number-specific structures and functions that are difficult to achieve with bottom-up synthesis methods. In particular, precisely etching metal atoms one by one from nonmetallic element-centred metal clusters and elucidating the relationship between their well-defined structures, and chemical and physical properties will facilitate future materials design for metal clusters. Here we report the single-gold etching at a hypercarbon centre in gold(I) clusters. Specifically, C-centred hexagold(I) clusters protected by chiral N-heterocyclic carbenes are etched with bisphosphine to yield C-centred pentagold(I) (CAuI5) clusters. The CAuI5 clusters exhibit an unusually large bathochromic shift in luminescence, which is reproduced theoretically. The etching mechanism is experimentally and theoretically suggested to be a tandem dissociation-association-elimination pathway. Furthermore, the vacant site of the central carbon of the CAuI5 cluster can accommodate AuCl, allowing for post-functionalisation of the C-centred gold(I) clusters.

Suggested Citation

  • 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.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-49295-w
    DOI: 10.1038/s41467-024-49295-w
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    References listed on IDEAS

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    1. Qiaofeng Yao & Yan Feng & Victor Fung & Yong Yu & De-en Jiang & Jun Yang & Jianping Xie, 2017. "Precise control of alloying sites of bimetallic nanoclusters via surface motif exchange reaction," Nature Communications, Nature, vol. 8(1), pages 1-11, December.
    2. Zhen Lei & Mizuki Endo & Hitoshi Ube & Takafumi Shiraogawa & Pei Zhao & Koichi Nagata & Xiao-Li Pei & Tomoya Eguchi & Toshiaki Kamachi & Masahiro Ehara & Takeaki Ozawa & Mitsuhiko Shionoya, 2022. "N-Heterocyclic carbene-based C-centered Au(I)-Ag(I) clusters with intense phosphorescence and organelle-selective translocation in cells," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. 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.
    4. Yitao Cao & Tongyu Liu & Tiankai Chen & Bihan Zhang & De-en Jiang & Jianping Xie, 2021. "Revealing the etching process of water-soluble Au25 nanoclusters at the molecular level," Nature Communications, Nature, vol. 12(1), pages 1-7, December.
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