A1 Journal article (refereed)
Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters (2024)
Deng, G., Malola, S., Ki, T., Liu, X., Yoo, S., Lee, K., Bootharaju, M. S., Häkkinen, H., & Hyeon, T. (2024). Structural Isomerism in Bimetallic Ag20Cu12 Nanoclusters. Journal of the American Chemical Society, Early online. https://doi.org/10.1021/jacs.4c06832
JYU authors or editors
Publication details
All authors or editors: Deng, Guocheng; Malola, Sami; Ki, Taeyoung; Liu, Xiaolin; Yoo, Seungwoo; Lee, Kangjae; Bootharaju, Megalamane S.; Häkkinen, Hannu; Hyeon, Taeghwan
Journal or series: Journal of the American Chemical Society
ISSN: 0002-7863
eISSN: 1520-5126
Publication year: 2024
Publication date: 18/09/2024
Volume: Early online
Publisher: American Chemical Society (ACS)
Publication country: United States
Publication language: English
DOI: https://doi.org/10.1021/jacs.4c06832
Publication open access: Not open
Publication channel open access:
Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/97125
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≡CR)24 (denoted as Ag20Cu12-1 and Ag20Cu12-2; HC≡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≡CR, one Cu(C≡CR)2, one Ag3Cu3(C≡CR)6, and two Cu2(C≡CR)4 units. Ag20Cu12-2 features a bitetrahedron Ag14 core, which is stabilized by three Ag2Cu4(C≡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.
Keywords: crystals; gold; hydrocarbons
Free keywords: crystal structure; gold; hydrocarbons; molecular structure; nanoclusters
Contributing organizations
Ministry reporting: Yes
VIRTA submission year: 2024
Preliminary JUFO rating: 3