Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes
Shen, H., Wang, L., López-Estrada, O., Hu, C., Wu, Q., Cao, D., Malola, S., Teo, B. K., Häkkinen, H., & Zheng, N. (2021). Copper-hydride nanoclusters with enhanced stability by N-heterocyclic carbenes. Nano Research, 14(9), 3303-3308. https://doi.org/10.1007/s12274-021-3389-9
Published inNano Research
© The Author(s) 2021
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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Related funder(s)Academy of Finland
Funding program(s)Research costs of Academy Professor, AoF; Research post as Academy Professor, AoF
Additional information about fundingWe 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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