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Nano Research 2021, 14(9): 3303-3308 https://doi.org/10.1007/s12274-021-3389-9
Research Article | Open Access | Issue | Published: 23 March 2021

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

Show Author's Information 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
Keywords:
stability, metal clusters, copper-hydride, N-heterocylic carbene, superatom
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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
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Abstract Full text Electronic supplementary material About this article

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.


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About this article

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

Show Author's information 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

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: stability, metal clusters, copper-hydride, N-heterocylic carbene, superatom

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Publication history

Received: 25 December 2020
Revised: 05 February 2021
Accepted: 08 February 2021
Published: 23 March 2021
Issue date: September 2021

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© The Author(s) 2021

Acknowledgements

We thank the National Key R&D Program of China (No. 2017YFA0207302), the National Natural Science Foundation of China (Nos. 21890752, 21731005, 21420102001, and 21721001) and the 111 Project (No. B08027) for financial support. The computational work in the University of Jyväskylä was supported by the Academy of Finland through HH’s Academy Professorship and grants 292352, 319208. H. H. acknowledges support from China’s National Innovation and Intelligence Introduction Base visitor program. The computations were made at the CSC supercomputing center in Finland. We thank L. Feng from High-Field Nuclear Magnetic Resonance Research Center (Xiamen University) for the help in the NMR studies.

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