Synthesis of RhH-doped Au-Ag alloy nanoclusters and dopant evolution.
Nanoscale
; 16(9): 4851-4857, 2024 Feb 29.
Article
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| MEDLINE
| ID: mdl-38314888
ABSTRACT
Doping atomically precise metal nanoclusters (NCs) with heterometals is a powerful method for tuning the physicochemical properties of the original NCs at the atomic level. While the heterometals incorporated into metal NCs are limited to group 10-12 metals with closed d-shells, the doping of open d-shell metals remains largely unexplored. Herein, we report the synthesis of Rh-doped Au-Ag alloy NCs by a metal-exchange reaction of [RhHAg24(SPhMe2)18]2- NCs with an Au-thiolate complex. Combined experimental and theoretical structural studies revealed that the synthesized product is a dianionic [RhHAuxAg24-x(SPhMe2)18]2- NC (x = 8-12), consisting of RhH dopant, Au-rich kernel, and Ag-thiolate staple motifs, with the superatomic 8-electron configuration (1S21P6). Under aerobic conditions, the synthesized NCs underwent kernel evolution to generate a 6-electron [RhAuxAg24-x(SPhMe2)18]1- NC (1S21P4), which was initiated by the desorption of hydride from the kernel. Structural analysis of the [RhHAuxAg24-x(SPhMe2)18]2- NC suggests that the kernel evolution is induced by the change in chemical bonds surrounding the hydride in the Au-rich kernel.
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01-internacional
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MEDLINE
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En
Revista:
Nanoscale
Año:
2024
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Article
Pais de publicación:
Reino Unido