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Layer-by-layer alloying of NIR-II emissive M50 (Au/Ag/Cu) superatomic nanocluster

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Abstract

The intermetallic synergy plays a critical role in exploring the chemical-physical properties of metal nanoclusters. However, the controlled doping or layer-by-layer alloying of atom-precise metal nanoclusters (NCs) has long been a challenging pursuit. In this work, two novel alloy nanoclusters [PPh4]4[Ag32Cu18(PFBT)36] ((AgCu)50) and [PPh4]4[Au12Ag20Cu18(PFBT)36] (Au12(AgCu)38), where PFBT is pentafluorobenzenethiolate, with shell-by-shell configuration of M12@Ag20@Cu18(PFBT)36 (M = Ag/Au) were synthesized by a facile one-pot co-reduction method. Notably, a fingerprint library of [Ag50−xCux(PFBT)36]4− (x = 0 to 50) from Ag50 to Cu50 has been successfully established as revealed by electrospray ionization mass spectrometry. Single-crystal X-ray diffraction analysis of trimetallic Au12(AgCu)38 confirmed the layer-by-layer alloying under reducing conditions. What is more, (AgCu)50 and Au12(AgCu)38 both show broad photoluminescence (PL) peak in the second near-infrared (NIR-II) window, and the Au doping in the innermost shell considerably enhances the photoluminescence intensity. This work not only offers an insight in the process of metal cluster alloying but also provides a platform to study the doping-directed PL properties in the multimetallic cluster system.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 92061201, 21825106, and 21801228), the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (No. 19IRTSTHN022) and Zhengzhou University.

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Authors and Affiliations

  1. Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China

    Xiao-Hong Ma, Jing-Tao Jia, Peng Luo, Zhao-Yang Wang, Shuang-Quan Zang & Thomas C. W. Mak

  2. Department of Chemistry, The Chinese University of Hong Kong, Hong Kong, 999077, China

    Thomas C. W. Mak

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  1. Xiao-Hong Ma
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  2. Jing-Tao Jia
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  3. Peng Luo
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  4. Zhao-Yang Wang
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  5. Shuang-Quan Zang
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Correspondence to Zhao-Yang Wang or Shuang-Quan Zang.

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Ma, XH., Jia, JT., Luo, P. et al. Layer-by-layer alloying of NIR-II emissive M50 (Au/Ag/Cu) superatomic nanocluster. Nano Res. 15, 5569–5574 (2022). https://doi.org/10.1007/s12274-022-4162-4

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