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Luminescence modulation of ultrasmall gold clusters by aromatic ligands

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Abstract

Luminescence is one of the most important properties for metal nanoclusters; however, clearly revealing its origin remains challenging. The different luminescence properties of the two prototypical 8e nanoclusters Au11 and Au13 remain elusive—Au11 is always nonluminescent, whereas Au13 is luminescent. In this work, by using a designed unique aromatic ligand (quinoline-2-thiol), we obtained new atomically precise phosphine-thiolate-protected neutral Au11-SH and cationic Au13-SH. In comparison with the classic phosphine-halide-protected Au11-Cl and Au13-Cl, the Cl-to-thiol alteration triggered room-temperature luminescence of the Au11 core and dramatically modulated that of the Au13 core. Ultrafast ultraviolet/infrared (UV/IR) spectroscopy, which is sensitive to organic aromatic groups, together with ultrafast transient absorption (TA) spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters. This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands, which would have direct applications in lighting, light harvesting, and photocatalysis.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. U21A20277, 92061201, 21825106, 21975065, 12174012, 22203006, and 22103072) and Zhengzhou University. The authors thank for the support of parallel high performance computing of National Supercomputing Center in Zhengzhou.

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  1. Xue-Jing Zhai, Jia-Hua Hu, and Jianxin Guan contributed equally to this work.

Authors and Affiliations

  1. College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China

    Xue-Jing Zhai, Jia-Hua Hu, Yubing Si, Xi-Yan Dong, Runping Han & Shuang-Quan Zang

  2. College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo, 454003, China

    Xue-Jing Zhai, Xi-Yan Dong & Peng Luo

  3. College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Jianxin Guan & Zhihao Yu

  4. College of Chemistry, Central China Normal University, Wuhan, 430079, China

    Fangfang Pan

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Zhai, XJ., Hu, JH., Guan, J. et al. Luminescence modulation of ultrasmall gold clusters by aromatic ligands. Nano Res. 16, 11366–11374 (2023). https://doi.org/10.1007/s12274-023-5817-5

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