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Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters

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Authors

Deng, Guocheng; Malola, Sami; Ki, Taeyoung; Liu, Xiaolin; Yoo, Seungwoo; Lee, Kangjae; Bootharaju, Megalamane S.; Hakkinen, Hannu; Hyeon, Taeghwan

Issue Date
2024-09
Publisher
American Chemical Society
Citation
Journal of the American Chemical Society, Vol.146 No.39, pp.26751-26758
Abstract
Structural isomers of atomically precise metal nanoclusters are highly sought after for investigating structure-property relationships in nanostructured materials. However, they are extremely rare, particularly those of alloys, primarily due to the challenges in their synthesis and structural characterization. Herein, for the first time, a pair of bimetallic isomeric AgCu nanoclusters has been controllably synthesized and structurally characterized. These two isomers share an identical molecular formula, Ag20Cu12(C equivalent to CR)(24) (denoted as Ag20Cu12-1 and Ag20Cu12-2; HC equivalent to CR is 3,5-bis(trifluoromethyl)phenylacetylene). Single-crystal X-ray diffraction data analysis revealed that Ag20Cu12-1 possesses an Ag17Cu4 core composed of two interpenetrating hollow Ag11Cu2 structures. This core is stabilized by four different types of surface motifs: eight -C equivalent to CR, one Cu(C equivalent to CR)(2), one Ag3Cu3(C equivalent to CR)(6), and two Cu-2(C equivalent to CR)(4) units. Ag20Cu12-2 features a bitetrahedron Ag-14 core, which is stabilized by three Ag2Cu4(C equivalent to CR)(8) units. Interestingly, Ag20Cu12-2 undergoes spontaneous transformation to Ag20Cu12-1 in the solution-state. Density functional theory calculations explain the electronic and optical properties and confirm the higher relative stability of Ag20Cu12-1 compared to Ag20Cu12-2. The controlled synthesis and structural isomerism of alloy nanoclusters presented in this work will stimulate and broaden research on nanoscale isomerism.
ISSN
0002-7863
URI
https://hdl.handle.net/10371/211227
DOI
https://doi.org/10.1021/jacs.4c06832
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  • School of Chemical and Biological Engineering
Research Area Chemistry, Materials Science

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