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Single thiolate replacement of metal nanoclusters

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Abstract

Surface thiolates play important roles in evincing the structures and properties of thiolated metal nanoclusters—one type of recently emerging inorganic-organic hybrids, and thus the thiolate substitution, especially single thiolate substitution, is highly desirable for subtly tailoring the structures and properties of metal nanoclusters. However, such a single-thiolate substituting is challenging, and its influence on the metal-metal and metal-sulfur bonds remains mysterious due to the absence of the single-thiolate-substituted structure. Here, we developed a combined method, concurrently synthesized the single-thiolate-substituted nanocluster and its parent nanocluster, and successfully resolved their structures by single crystal X-ray crystallography, which reveals that the single thiolate substitute has an obvious influence on the metal-metal and metal-sulfur bond lengths although it has no effect on the absorption profile. Interestingly, the metal-metal and metal-sulfur bonds show various thermal extensibility and even the negative thermal expansion phenomena of the Au–S bond were observed in the single-thiolate-substituted nanocluster. The bond length-related stability was also observed. Overall, this study highlights a novel synthesis method and offers novel structural insights and an in-depth structure-property correlation of thiolated metal nanoclusters.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21925303, 21829501, 21771186, 22171268, 22171267, 21971246), the Anhui Provincial Natural Science Foundation (2108085MB56), the HFIPS Director’s Fund (BJPY2019A02, YZJJ202102, YZJJ202306-TS) and the Collaborative Innovation Program of Hefei Science Center, Chinese Academy of Sciences (2020HSC-CIP005, 2022HSC-CIP018). Ambreen thanks Mr Z. Gan and Mr S. Ji for their help and supports.

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Authors and Affiliations

  1. Key Laboratory of Materials Physics, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Hefei Institutes of Physical Science (HFIPS), Chinese Academy of Sciences, Hefei, 230031, China

    Ambreen Ambreen, Yue Zhou, Wanmiao Gu, Qing You, Liang Fang, Guoqing Bian, Nan Yan, Nan Xia & Zhikun Wu

  2. University of Science and Technology of China, Hefei, 230601, China

    Ambreen Ambreen, Yue Zhou, Liang Fang & Guoqing Bian

  3. Institute of Physical Science and Information Technology, Anhui University, Hefei, 230601, China

    Wanmiao Gu, Qing You, Nan Yan, Nan Xia & Zhikun Wu

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  1. Ambreen Ambreen
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  2. Yue Zhou
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  3. Wanmiao Gu
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  4. Qing You
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Correspondence to Nan Xia or Zhikun Wu.

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Supporting information The supporting information is available online at chem.scichina.com and link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Ambreen, A., Zhou, Y., Gu, W. et al. Single thiolate replacement of metal nanoclusters. Sci. China Chem. 67, 523–528 (2024). https://doi.org/10.1007/s11426-023-1775-y

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  • DOI: https://doi.org/10.1007/s11426-023-1775-y

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