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Research Article

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

Xiao-Hong Ma1, Jing-Tao Jia1, Peng Luo1, Zhao-Yang Wang1( ), Shuang-Quan Zang1( ), Thomas C. W. Mak1,2
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
Department of Chemistry, The Chinese University of Hong Kong, Hong Kong 999077, China
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Graphical Abstract

A bimetallic nanocluster (AgCu)50 with a shell-by-shell configuration of Ag12@Ag20@Cu18wassynthesized by a facile one-pot co-reduction method, and the preparation established a fingerprintlibrary of Ag50−xCux (x = 0 to 50) from Ag50 to Cu50 as revealed by electrospray ionization massspectrum (ESI-MS). Under adjusted reducing conditions, the innermost Ag12 icosahedron in(AgCu)50 has been selectively substituted by Au12, yielding the isostructural trimetallicAu12(AgCu)38with each layer containing different metals, suggesting a layer-by-layer alloyingroutine. (AgCu)50and Au12(AgCu)38 both show a broad photoluminescence (PL) peak in the secondnear infrared (NIR-II) region, while the luminescence intensity of the Au-doped Au12(AgCu)38 is15-fold enhanced in comparison to that of (AgCu)50.

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.

Keywords

alloy nanoclustersecond near infrared (NIR-II) emissionsuperatomdoping

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Nano Research
Volume 15 Issue 6,
June 2022
Pages 5569-5574
DOI: 10.1007/s12274-022-4162-4
Cite this article:
Ma X-H, Jia J-T, Luo P, et al. Layer-by-layer alloying of NIR-II emissive M50 (Au/Ag/Cu) superatomic nanocluster. Nano Research, 2022, 15(6): 5569-5574. https://doi.org/10.1007/s12274-022-4162-4
Topics:
Nanoclusters

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Received: 10 September 2021
Revised: 16 January 2022
Accepted: 17 January 2022
Published: 10 March 2022
© Tsinghua University Press 2022
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