Issue 14, 2024

Doping effect on a two-electron silver nanocluster

Abstract

This study investigates the effects of metal addition and doping of a 2-electron silver superatom, [Ag10{S2P(OiPr)2}8] (Ag10). When Ag+ is added to Ag10 in THF solution, [Ag11{S2P(OiPr)2}8(OTf)] (Ag11) is rapidly formed almost quantitatively. When the same method is used with Cu+, a mixture of alloys, [CuxAg11−x{S2P(OiPr)2}8]+ (x = 1–3, CuxAg11−x), is obtained. In contrast, introducing Au+ to Ag10 leads to decomposition. The structural and compositional analysis of Ag11 was characterized by single-crystal X-ray diffraction (SCXRD), ESI-MS, NMR spectroscopy, and DFT calculations. While no crystal structure was obtained for CuxAg11−x, DFT calculations provide insights into potential sites for copper location. The absorption spectrum exhibits a notable blue shift in the low-energy band after copper doping, contrasting with that of the slight shift observed in 8-electron Cu-doped Ag nanoclusters. Ag11 and CuxAg11−x are strongly emissive at room temperature, and solvatochromism across different organic solvents is highlighted. This study underscores the profound influence of metal addition and doping on the structural and optical properties of silver nanoclusters, providing important contributions to understanding the nanoclusters and their photophysical behaviors.

Graphical abstract: Doping effect on a two-electron silver nanocluster

Supplementary files

Article information

Article type
Paper
Submitted
22 Gen. 2024
Accepted
05 Meur. 2024
First published
05 Meur. 2024

Nanoscale, 2024,16, 7011-7018

Doping effect on a two-electron silver nanocluster

W. Yen, J. Liao, T. Chiu, J. Chen, Y. J. Chen, S. Kahlal, J. Saillard and C. W. Liu, Nanoscale, 2024, 16, 7011 DOI: 10.1039/D4NR00326H

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