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...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 Cu3i(RS)25(NHC)3H6(NHC=1,4-bis(1-benzyl-1 H-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.展开更多
Phase engineering has been emerging as an effective strategy to tune the properties of two-dimensional transition-metal dichalcogenides(TMDs)for a variety of applications including electronics,catalysis,energy storage...Phase engineering has been emerging as an effective strategy to tune the properties of two-dimensional transition-metal dichalcogenides(TMDs)for a variety of applications including electronics,catalysis,energy storage and membrane separation[1].展开更多
基金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 supportsupported by the Academy of Finland through HHs Academy Professorship and grants 292352,319208.
文摘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 Cu3i(RS)25(NHC)3H6(NHC=1,4-bis(1-benzyl-1 H-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.
基金support by the National Natural Science Foundation of China(21890752 and 92261207)support from IKKEMthe support from the New Cornerstone Science Foundation through the XPLORER PRIZE。
文摘Phase engineering has been emerging as an effective strategy to tune the properties of two-dimensional transition-metal dichalcogenides(TMDs)for a variety of applications including electronics,catalysis,energy storage and membrane separation[1].
