AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
PDF (8.4 MB)
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript AI Chat Paper
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article | Open Access

Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes

Hui Shen1, Lingzheng Wang1, Omar López-Estrada2, Chengyi Hu1, Qingyuan Wu1, Dongxu Cao1, Sami Malola2, Boon K. Teo1, Hannu Häkkinen2( ), Nanfeng Zheng1( )
State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National & Local Joint Engineering Research Center of Preparation Technology of Nanomaterials, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä, Finland
Show Author Information

Graphical Abstract

Abstract

Copper-hydrides have been intensively studied for a long time due to their utilization in a variety of technologically important chemical transformations. Nevertheless, poor stability of the species severely hinders its isolation, storage and operation, which is worse for nano-sized ones. We report here an unprecedented strategy to access to ultrastable copper-hydride nanoclusters (NCs), namely, using bidentate N-heterocyclic carbenes as stabilizing ligands in addition to thiolates. In this work, a simple synthetic protocol was developed to synthesize the first large copper-hydride nanoclusters (NCs) stabilized by N-heterocyclic carbenes (NHCs). The NC, with the formula of Cu31(RS)25(NHC)3H6 (NHC = 1,4-bis(1-benzyl-1H-benzimidazol-1-ium-3-yl) butane, RS = 4-fluorothiophenol), was fully characterized by high resolution Fourier transform ion cyclotron resonance mass spectrum, nuclear magnetic resonance, ultra-violet visible spectroscopy, density functional theory (DFT) calculations and single-crystal X-ray crystallography. Structurally, the title cluster exhibits unprecedented Cu4 tetrahedron-based vertex-sharing (TBVS) superstructure (fusion of six Cu4 tetrahedra). Moreover, the ultrahigh thermal stability renders the cluster a model system to highlight the power of NHCs (even other carbenes) in controlling geometrical, electronic and surface structure of polyhydrido copper clusters.

Keywords

metal clusterscopper-hydrideN-heterocylic carbenestabilitysuperatom

Electronic Supplementary Material

Download File(s)
12274_2021_3389_MOESM1_ESM.pdf (3.5 MB)
12274_2021_3389_MOESM2_ESM.mpg (22.2 MB)
12274_2021_3389_MOESM3_ESM.mpg (21.6 MB)

References

[1]
Shi, S. L.; Wong, Z. L.; Buchwald, S. L. Copper-catalysed enantioselective stereodivergent synthesis of amino alcohols. Nature 2016, 532, 353-356.
Crossref Google Scholar
[2]
Yang, Y.; Shi, S. L.; Niu, D. W.; Liu, P.; Buchwald, S. L. Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines. Science 2015, 349, 62-66.
Crossref Google Scholar
[3]
Zhu, S. L.; Niljianskul, N.; Buchwald, S. L. A direct approach to amines with remote stereocentres by enantioselective CuH-catalysed reductive relay hydroamination. Nat. Chem. 2016, 8, 144-150.
Crossref Google Scholar
[4]
Zall, C. M.; Linehan, J. C.; Appel, A. M. Triphosphine-ligated copper hydrides for CO2 hydrogenation: Structure, reactivity, and thermodynamic studies. J. Am. Chem. Soc. 2016, 138, 9968-9977.
Crossref Google Scholar
[5]
Jordan, A. J.; Lalic, G.; Sadighi, J. P. Coinage metal hydrides: Synthesis, characterization, and reactivity. Chem. Rev. 2016, 116, 8318-8372.
Crossref Google Scholar
[6]
Sun, C. F.; Mammen, N.; Kaappa, S.; Yuan, P.; Deng, G. C.; Zhao, C. W.; Yan, J. Z.; Malola, S.; Honkala, K.; Häkkinen, H. et al. Atomically precise, thiolated copper-hydride nanoclusters as single-site hydrogenation catalysts for ketones in mild conditions. ACS Nano 2019, 13, 5975-5986.
Crossref Google Scholar
[7]
Bezman, S. A.; Churchill, M. R.; Osborn, J. A.; Wormald, J. Preparation and crystallographic characterization of a hexameric triphenylphosphinecopper hydride cluster. J. Am. Chem. Soc. 1971, 93, 2063-2065.
Crossref Google Scholar
[8]
Lipshutz, B. H.; Frieman, B. A. CuH in a bottle: A convenient reagent for asymmetric hydrosilylations. Angew. Chem., Int. Ed. 2005, 44, 6345-6348.
Crossref Google Scholar
[9]
Mahoney, W. S.; Brestensky, D. M.; Stryker, J. M. Selective hydride-mediated conjugate reduction of α,β-unsaturated carbonyl compounds using [(Ph3P)CuH]6. J. Am. Chem. Soc. 1988, 110, 291-293.
Crossref Google Scholar
[10]
Lemmen, T. H.; Foiling, K.; Huffman, J. C.; Caulton, K. G. Copper polyhydrides. J. Am. Chem. Soc. 1985, 107, 7774-7775.
Crossref Google Scholar
[11]
Yuan, P.; Chen, R. H.; Zhang, X. M.; Chen, F. J.; Yan, J. Z.; Sun, C. F.; Ou, D. H.; Peng, J.; Lin, S. C.; Tang, Z. C. et al. Ether-soluble Cu53 nanoclusters as an effective precursor of high-quality CuI films for optoelectronic applications. Angew. Chem., Int. Ed. 2019, 58, 835-839.
Google Scholar
[12]
Liao, P. K.; Fang, C. S.; Edwards, A. J.; Kahlal, S.; Saillard, J. Y.; Liu, C. W. Hydrido copper clusters supported by dithiocarbamates: Oxidative hydride removal and neutron diffraction analysis of [Cu7(H){S2C(aza-15-crown-5)}6]. Inorg. Chem. 2012, 51, 6577-6591.
Google Scholar
[13]
Edwards, A. J.; Dhayal, R. S.; Liao, P. K.; Liao, J. H.; Chiang, M. H.; Piltz, R. O.; Kahlal, S.; Saillard, J. Y.; Liu, C. W. Chinese puzzle molecule: A 15 hydride, 28 copper atom nanoball. Angew. Chem., Int. Ed. 2014, 53, 7214-7218.
Google Scholar
[14]
Dhayal, R. S.; Liao, J. H.; Kahlal, S.; Wang, X. P.; Liu, Y. C.; Chiang, M. H.; van Zyl, W. E.; Saillard, J. Y.; Liu, C. W. [Cu32(H)20{S2P(OiPr)2}12]: The largest number of hydrides recorded in a molecular nanocluster by neutron diffraction. Chem.—Eur. J. 2015, 21, 8369-8374.
Google Scholar
[15]
Dhayal, R. S.; Liao, J. H.; Wang, X. P.; Liu, Y. C.; Chiang, M. H.; Kahlal, S.; Saillard, J. Y.; Liu, C. W. Diselenophosphate-induced conversion of an achiral [Cu20H11{S2P(OiPr)2}9] into a chiral [Cu20H11{Se2P(OiPr)2}9] polyhydrido nanocluster. Angew. Chem., Int. Ed. 2015, 54, 13604-13608.
Google Scholar
[16]
Lee, S.; Bootharaju, M. S.; Deng, G.; Malola, S.; Baek, W.; Häkkinen, H.; Zheng, N. F.; Hyeon, T. [Cu32(PET)24H8Cl2](PPh4)2: A copper hydride nanocluster with a bisquare antiprismatic core. J. Am. Chem. Soc. 2020, 142, 13974-13981.
Google Scholar
[17]
Huang, R. W.; Yin, J.; Dong, C. W.; Ghosh, A.; Alhilaly, M. J.; Dong, X. L.; Hedhili, M. N.; Abou-Hamad, E.; Alamer, B.; Nematulloev, S. et al. [Cu81(PhS)46(tBuNH2)10(H)32]3+ reveals the coexistence of large planar cores and hemispherical shells in high-nuclearity copper nanoclusters. J. Am. Chem. Soc. 2020, 142, 8696-8705.
Google Scholar
[18]
Li, J. Y.; Ma, H. Z.; Reid, G. E.; Edwards, A. J.; Hong, Y. N.; White, J. M.; Mulder, R. J.; O'Hair, R. A. J. Synthesis and X-ray crystallographic characterisation of frustum-shaped ligated [Cu18H16(DPPE)6]2+ and [Cu16H14(DPPA)6]2+ nanoclusters and studies on their H2 evolution reactions. Chem.—Eur. J. 2018, 24, 2070-2074.
Google Scholar
[19]
Nguyen, T. A.; Jones, Z. R.; Goldsmith, B. R.; Buratto, W. R.; Wu, G.; Scott, S. L.; Hayton, T. W. A Cu25 nanocluster with partial Cu(0) character. J. Am. Chem. Soc. 2015, 137, 13319-13324.
Google Scholar
[20]
Sun, C. F.; Teo, B. K.; Deng, C. L.; Lin, J. Q.; Luo, G. G.; Tung, C. H.; Sun, D. Hydrido-coinage-metal clusters: Rational design, synthetic protocols and structural characteristics. Coordin. Chem. Rev. 2021, 427, 213576.
Google Scholar
[21]
Hopkinson, M. N.; Richter, C.; Schedler, M.; Glorius, F. An overview of N-heterocyclic carbenes. Nature 2014, 510, 485-496.
Google Scholar
[22]
Smith, C. A.; Narouz, M. R.; Lummis, P. A.; Singh, I.; Nazemi, A.; Li, C. H.; Crudden, C. M. N-Heterocyclic carbenes in materials chemistry. Chem. Rev. 2019, 119, 4986-5056.
Google Scholar
[23]
Zhao, Q.; Meng, G. R.; Nolan, S. P.; Szostak, M. N-Heterocyclic carbene complexes in C-H activation reactions. Chem. Rev. 2020, 120, 1981-2048.
Google Scholar
[24]
Zhukhovitskiy, A. V.; MacLeod, M. J.; Johnson, J. A. Carbene ligands in surface chemistry: From stabilization of discrete elemental allotropes to modification of nanoscale and bulk substrates. Chem. Rev. 2015, 115, 11503-11532.
Google Scholar
[25]
Robilotto, T. J.; Bacsa, J.; Gray, T. G.; Sadighi, J. P. Synthesis of a trigold monocation: An isolobal analogue of [H3]+. Angew. Chem., Int. Ed. 2012, 51, 12077-12080.
Google Scholar
[26]
Jin, L. Q.; Weinberger, D. S.; Melaimi, M.; Moore, C. E.; Rheingold, A. L.; Bertrand, G. Trinuclear gold clusters supported by cyclic (alkyl)(amino)carbene ligands: Mimics for gold heterogeneous catalysts. Angew. Chem., Int. Ed. 2014, 53, 9059-9063.
Google Scholar
[27]
Narouz, M. R.; Osten, K. M.; Unsworth, P. J.; Man, R. W. Y.; Salorinne, K.; Takano, S.; Tomihara, R.; Kaappa, S.; Malola, S.; Dinh, C. T. et al. N-Heterocyclic carbene-functionalized magic-number gold nanoclusters. Nat. Chem. 2019, 11, 419-425.
Google Scholar
[28]
Narouz, M. R.; Takano, S.; Lummis, P. A.; Levchenko, T. I.; Nazemi, A.; Kaappa, S.; Malola, S.; Yousefalizadeh, G.; Calhoun, L. A.; Stamplecoskie, K. G. et al. Robust, highly luminescent Au13 superatoms protected by N-heterocyclic carbenes. J. Am. Chem. Soc. 2019, 141, 14997-15002.
Google Scholar
[29]
Shen, H.; Xiang, S. J; Xu, Z.; Liu, C.; Li, X. H.; Sun, C. F.; Lin, S. C.; Teo, B. K.; Zheng, N. F. Superatomic Au13 clusters ligated by different N-heterocyclic carbenes and their ligand-dependent catalysis, photoluminescence, and proton sensitivity. Nano Res. 2020, 13, 1908-1911.
Google Scholar
[30]
Shen, H.; Deng, G. C.; Kaappa, S.; Tan, T. D.; Han, Y. Z.; Malola, S.; Lin, S. C.; Teo, B. K.; Hakkinen, H.; Zheng, N. F. Highly robust but surface-active: An N-heterocyclic carbene-stabilized Au25 nanocluster. Angew. Chem., Int. Ed. 2019, 58, 17731-17735.
Google Scholar
[31]
Shen, H.; Xu, Z.; Hazer, M. S. A.; Wu, Q. Y.; Peng, J.; Qin, R. X.; Malola, S.; Teo, B. K.; Häkkinen, H.; Zheng, N. F. Surface coordination of multiple ligands endows N-heterocyclic carbene-stabilized gold nanoclusters with high robustness and surface reactivity. Angew. Chem., Int. Ed. 2021, 133, 3796-3802.
Google Scholar
[32]
Khalili Najafabadi, B. Corrigan, J. F. N-Heterocyclic carbene stabilized Ag-P nanoclusters. Chem. Commun. 2015, 51, 665-667.
Google Scholar
[33]
Peltier, J. L.; Soleilhavoup, M.; Martin, D.; Jazzar, R.; Bertrand, G. Absolute templating of M(111) cluster surrogates by galvanic exchange. J. Am. Chem. Soc. 2020, 142, 16479-16485.
Google Scholar
[34]
Makarem, A.; Berg, R.; Rominger, F.; Straub, B. F. A fluxional copper acetylide cluster in CuAAC catalysis. Angew. Chem., Int. Ed. 2015, 54, 7431-7435.
Google Scholar
[35]
Humenny, W. J.; Mitzinger, S.; Khadka, C. B.; Najafabadi, B. K.; Vieira, I.; Corrigan, J. F. N-Heterocyclic carbene stabilized copper- and silver-phenylchalcogenolate ring complexes. Dalton Trans. 2012, 41, 4413-4422.
Google Scholar
[36]
Drescher, W.; Borner, C.; Kleeberg, C. Stability and decomposition of copper(I) boryl complexes: [(IDipp)Cu-Bneop], [(IDipp*)Cu-Bneop] and copper clusters. New J. Chem., in press, .
Crossref Google Scholar
[37]
Chen, C.; Qiu, H. Y.; Chen, W. Z. Trinuclear copper(I) complex of 1,3-bis(2-pyridinylmethyl)imidazolylidene as a carbene-transfer reagent for the preparation of catalytically active nickel(II) and palladium(II) complexes. J. Organomet. Chem. 2012, 696, 4166-4172.
Google Scholar
[38]
Korotkikh, N. I.; Saberov, V. S.; Kiselev, A. V.; Glinyanaya, N. V.; Marichev, K. A.; Pekhtereva, T. M.; Dudarenko, G. V.; Bumagin, N. A.; Shvaika, O. P. Heterocyclic carbene complexes of nickel, palladium, and copper(I) as effective catalysts for the reduction of ketones. Chem. Heterocycl. Comp. 2012, 47, 1551-1560.
Google Scholar
[39]
Yuan, X. T.; Sun, C. F.; Li, X. H.; Malola, S.; Teo, B. K.; Häkkinen, H.; Zheng, L. S.; Zheng, N. F. Combinatorial identification of hydrides in a ligated Ag40 nanocluster with noncompact metal core. J. Am. Chem. Soc. 2019, 141, 11905-11911.
Google Scholar
[40]
Han, B. L.; Liu, Z.; Feng, L.; Wang, Z.; Gupta, R. K.; Aikens, C. M.; Tung, C. H.; Sun, D. Polymorphism in atomically precise Cu23 nanocluster incorporating tetrahedral [Cu4]0 kernel. J. Am. Chem. Soc. 2020, 142, 5834-5841.
Google Scholar
[41]
Zeng, C. J.; Chen, Y. X.; Liu, C.; Nobusada, K.; Rosi, N. L.; Jin, R. C. Gold tetrahedra coil up: Kekulé-like and double helical superstructures. Sci. Adv. 2015, 1, e1500425.
Google Scholar
[42]
Qu, M.; Zhang, F. Q.; Wang, D. H.; Li, H.; Hou, J. J.; Zhang, X. M. Observation of non-FCC copper in alkynyl-protected Cu53 nanoclusters. Angew. Chem., Int. Ed. 2020, 59, 6507-6512.
Google Scholar
[43]
Walter, M.; Akola, J.; Lopez-Acevedo, O.; Jadzinsky, P. D.; Calero, G.; Ackerson, C. J.; Whetten, R. L.; Grönbeck, H.; Häkkinen, H. A unified view of ligand-protected gold clusters as superatom complexes. Proc. Natl. Acad. Sci. USA 2008, 105, 9157-9162.
Google Scholar
[44]
Ghosh, A.; Huang, R. W.; Alamer, B.; Abou-Hamad, E.; Hedhili, M. N.; Mohammed, O. F.; Bakr, O. M. [Cu61(StBu)26S6Cl6H14]+: A core-shell superatom nanocluster with a Quasi-J36 Cu19 core and an “18-Crown-6” metal-sulfide-like stabilizing belt. ACS Materials Lett. 2019, 1, 297-302.
Google Scholar
[45]
Chen, A. L.; Kang, X.; Jin, S.; Du, W. J.; Wang, S. X.; Zhu, M. Z. Gram-scale preparation of stable hydride M@Cu24 (M = Au/Cu) nanoclusters. J. Phys. Chem. Lett. 2019, 10, 6124-6128.
Google Scholar
Nano Research
Volume 14 Issue 9,
September 2021
Pages 3303-3308
DOI: 10.1007/s12274-021-3389-9
Cite this article:
Shen H, Wang L, López-Estrada O, et al. Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes. Nano Research, 2021, 14(9): 3303-3308. https://doi.org/10.1007/s12274-021-3389-9
Topics:
Calculations
Part of a topical collection:
Seventh Nano Research Award

925

Views

31

Downloads

42

Crossref

36

Web of Science

39

Scopus

1

CSCD

Altmetrics
Received: 25 December 2020
Revised: 05 February 2021
Accepted: 08 February 2021
Published: 23 March 2021
© The Author(s) 2021

This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
Return