A1 Journal article (refereed)
[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core (2020)

Lee, S., Bootharaju, M. S., Deng, G., Malola, S., Baek, W., Häkkinen, H., Zheng, N., & Hyeon, T. (2020). [Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core. Journal of the American Chemical Society, 142(32), 13974-13981. https://doi.org/10.1021/jacs.0c06577

JYU authors or editors

Publication details

All authors or editors: Lee, Sanghwa; Bootharaju, Megalamane S.; Deng, Guocheng; Malola, Sami; Baek, Woonhyuk; Häkkinen, Hannu; Zheng, Nanfeng; Hyeon, Taeghwan

Journal or series: Journal of the American Chemical Society

ISSN: 0002-7863

eISSN: 1520-5126

Publication year: 2020

Volume: 142

Issue number: 32

Pages range: 13974-13981

Publisher: American Chemical Society

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/jacs.0c06577

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/71215


Atomically precise coinage metal (Au, Ag and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC, [Cu32(PET)24H8Cl2](PPh4)2 co-protected by 2-phenylethanethiolate (PET), hydride and chloride ligands. Its crystal structure comprises a rare bisquare antiprismatic Cu14H8 core, assembled by two square antiprisms by edge-sharing followed by hydride binding. The rod-shaped Cu14H8 core is clamped by two complex Cu7(PET)11Cl and two simple Cu2PET metal ligand frameworks, constructing the complete structure of Cu32 NC. The presence, number and location of hydrides are established by combined experimental and density functional theory results. The electronic structure calculations show the cluster as a zero-free-electron system, reproduce well the measured optical absorption spectrum and explain the main absorption features. Furthermore, the Cu32 cluster is found to be a highly active homogeneous catalyst for the C-N bond formation in aniline carbonylation reaction at room temperature. We hope that new findings in this work will stimulate and expand the research on Cu and other active metal NCs.

Keywords: copper; nanostructures; nanoparticles; clusters

Free keywords: Copper hydride nanocluster

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Ministry reporting: Yes

Reporting Year: 2020

JUFO rating: 3

Last updated on 2022-20-09 at 13:25