4.8 Article

Identifying the Real Chemistry of the Synthesis and Reversible Transformation of AuCd Bimetallic Clusters

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AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c05053

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资金

  1. Natural Science Foundation of Shaanxi Province [2021JM-048]
  2. Natural Science Foundation of Ningbo [202003N4005]
  3. Fundamental Rese arch Funds for the Central Universities [31020190QD013]
  4. National Natural Science Foundation of China [22103035, 22033005]
  5. Guangdong Provincial Key Laboratory of Catalysis [2020B121201002]
  6. Center for Computational Science and Engineering (SUSTech)

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The capability of precisely constructing bimetallic clusters with atomic accuracy provides exciting opportunities for establishing their structure-property correlations. However, the chemistry dictating the fabrication of clusters with atomic-level control has been a long-standing challenge. In this study, the factors of steric hindrance and electronic effect of ligands, the charge state of Au-25(SR)(18), and the amount of dopant were systematically investigated. The results revealed the reversible transformation between [Au19Cd3(SR)(18)](-) and Au24Cd(SR)(18) by manipulating ligands with different steric hindrances. Additionally, a novel bimetallic cluster, Au4Cd4(SR)(12), was successfully fabricated by introducing an excess amount of dopant.
The capability of precisely constructing bimetallic clusters with atomic accuracy provides exciting opportunities for establishing their structure-property correlations. However, the chemistry (the charge state of precursors, the property of ligands, the amount of dopant, and so forth) dictating the fabrication of clusters with atomic-level control has been a long-standing challenge. Herein, based on the well-defined Au-25(SR)(18) cluster (SR = thiolates), we have systematically investigated the factors of steric hindrance and electronic effect of ligands, the charge state of Au-25(SR)(18), and the amount of dopant that may determine the structure of AuCd clusters. It is revealed that [Au19Cd3(SR)(18)](-) can be obtained when a ligand of smaller steric hindrance is used, while Au24Cd(SR)(18) is attained when a larger steric hindrance ligand is used. In addition, negatively charged [Au-25(SR)(18)](-) is apt to form [Au19Cd3(SR)(18)](-) during Cd doping, while Au24Cd(SR)(18) is produced when neutral Au-25(SR)(18) is used as a precursor. Intriguingly, the reversible transformation between [Au19Cd3(SR)(18)](-) and Au24Cd(SR)(18) is feasible by subtly manipulating ligands with different steric hindrances. Most importantly, by introducing the excess amount of dopant, a novel bimetallic cluster, Au4Cd4(SR)(12) is successfully fabricated and its total structure is fully determined. The electronic structures and the chirality of Au4Cd4(SR)(12) have been elucidated by density functional theory (DFT) calculations. Au4Cd4(SR)(12) reported herein represents the smallest AuCd bimetallic cluster with chirality.

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