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Multiple Ways Realizing Charge‐State Transform in AuCu Bimetallic Nanoclusters with Atomic Precision
Author(s) -
Li Qinzhen,
Chai Jinsong,
Yang Sha,
Song Yongbo,
Chen Tao,
Chen Cheng,
Zhang Hui,
Yu Haizhu,
Zhu Manzhou
Publication year - 2021
Publication title -
small
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.785
H-Index - 236
eISSN - 1613-6829
pISSN - 1613-6810
DOI - 10.1002/smll.201907114
Subject(s) - nanoclusters , bimetallic strip , materials science , thermogravimetric analysis , photoluminescence , oxidation state , electrospray ionization , redox , paramagnetism , alloy , electron paramagnetic resonance , chemical physics , crystallography , mass spectrometry , nanotechnology , chemistry , metal , nuclear magnetic resonance , condensed matter physics , physics , organic chemistry , optoelectronics , metallurgy , chromatography
Thiolate‐protected nanoclusters with different charge states usually show similar structure frameworks but different electronic configurations, which are proved to dramatically affect their properties such as magnetism, photoluminescence, and catalytic activity. Until now, few nanoclusters with alterable charge states have been reported and only some of them are structurally solved, limiting the in‐depth studies on their interesting properties. Here, a new AuCu alloy nanocluster [Au 18 Cu 32 (SPhCl) 36 ] 2− (HSPhCl = 4‐chlorophenylthiophenol) is synthesized and structurally solved by X‐ray crystallography. Interestingly, it is found that this nanocluster can be reduced to another nanocluster with a different charge state, that is, [Au 18 Cu 32 (SPhCl) 36 ] 3− . This change in charge states is clearly proved by X‐ray crystallography, electrospray ionization mass spectrometry, thermogravimetric analysis, and electron paramagnetic resonance. Furthermore, several redox methods are carried out to realize the reversible interconversion between these two nanoclusters, including electrochemical redox, introduction of H 2 O 2 /NaBH 4 , and oxidation with silica under air atmosphere. This work offers new insight into the transform progress of charge states with AuCu alloy nanoclusters which contributes to the understanding of the relationship between electronic structure and properties of nanoclusters and further development of AuCu nanoclusters with excellent performance.