[Cu32(PET)24H8Cl2](PPh4)2: A Copper Hydride Nanocluster with a Bisquare Antiprismatic Core
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
Published inJournal of the American Chemical Society
© 2020 American Chemical Society
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. ...
PublisherAmerican Chemical Society
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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Research post as Academy Professor, AoF
Additional information about fundingT.H. acknowledges the financial support by the Research Center Program of the IBS (IBS-R006-D1) in Korea. N.F.Z. acknowledges the financial support by the National Key Research and Development Program of China (2017YFA0207302), and the National Natural Science Foundation of China (21890752, 21731005, 21721001). The theoretical work at University of Jyväskylä was supported by the Academy of Finland (grants 292352 and 319208). The computations were done at the JYU node of the Finnish FGCI computing infrastructure. T.H. acknowledges the financial support by the Research Center Program of the IBS (IBS-R006-D1) in Korea. N.F.Z. acknowledges the financial support by the National Key Research and Development Program of China (2017YFA0207302), and the National Natural Science Foundation of China (21890752, 21731005, 21721001). The theoretical work at University of Jyväskylä was supported by the Academy of Finland (grants 292352 and 319208). The computations were done at the JYU node of the Finnish FGCI computing infrastructure. ...
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