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 editorsLee, Sanghwa; Bootharaju, Megalamane S.; Deng, Guocheng; Malola, Sami; Baek, Woonhyuk; Häkkinen, Hannu; Zheng, Nanfeng; Hyeon, Taeghwan

Journal or seriesJournal of the American Chemical Society

ISSN0002-7863

eISSN1520-5126

Publication year2020

Volume142

Issue number32

Pages range13974-13981

PublisherAmerican Chemical Society

Publication countryUnited States

Publication languageEnglish

DOIhttps://doi.org/10.1021/jacs.0c06577

Publication open accessNot open

Publication channel open access

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


Abstract

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.


Keywordscoppernanostructuresnanoparticlesclusters

Free keywordsCopper hydride nanocluster


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Ministry reportingYes

Reporting Year2020

JUFO rating3


Last updated on 2024-26-03 at 09:18