| Autor: |
Cui, Mengting, Shi, Yanan, Ma, Xiangyu, Li, Qingliang, Chen, Ling, Zhang, Lichao, Wu, Junfei, Yu, Haizhu, Zhu, Manzhou |
| Zdroj: |
ACS Nano; February 2024, Vol. 18 Issue: 8 p6591-6599, 9p |
| Abstrakt: |
The atomic precision of sub-nanometer-sized metal nanoclusters makes it possible to elucidate the kinetics of metal nanomaterials from the molecular level. Herein, the size reduction of an atomically precise [Au23(CHT)16]−(HCHT = cyclohexanethiol) cluster upon ligand exchange with HSAdm (1-adamantanethiol) has been reported. During the 16 h conversion of [Au23(CHT)16]−to Au16(SR)12, the neutral 6e Au21(SR)15, and its 1e-reduction state, i.e. the 5e, cationic radical, [Au21(SR)15]+, are active intermediates to account for the formation of thermodynamically stable Au16products. The combination of spectroscopic monitoring (with UV–vis and ESI-MS) and DFT calculations indicates the preferential size-reduction on the corner Au atoms on the core surface and the terminal Au atoms on longer AunSn+1staples. This study provides a reassessment on the electronic state of the Au21structure and highlights the single electron transfer processes in cluster systems and thus the importance of the EPR analysis on the mechanistic issues. |
| Databáze: |
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