Superatomic Au13 clusters ligated by different N-heterocyclic carbenes and their ligand-dependent catalysis, photoluminescence, and proton sensitivity

Shen, Hsin‐Hui; Xiang, Sijin; Xu, Zhen; Liu, Chen; Li, Xihua; Sun, Cunfa; Lin, Shuichao; Teo, Boon K.; Zheng, Nanfeng

doi:10.1007/s12274-020-2685-0

Cited by 93 publications

(161 citation statements)

References 30 publications

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“…65,85 Following the above report, Au superatoms protected only by other NHCs and halogens have been reported. [86][87][88] For example, [Au 13 (NHC Bn ) 9 Cl 3 ] 2+ (NHC Bn = C 7 H 4 N 2 (CH 2 Ph) 2 ) ( Fig. 6b) 86 and [Au 13 (di-NHC) 5 Br 2 ] 3+ (di-NHC = PhCH 2 -C 7 H 4 N 2 -(CH 2 ) 3 -C 7 H 4 N 2 -CH 2 Ph) ( Fig.…”

Section: Improving Robustnessmentioning

confidence: 99%

“…6b) 86 and [Au 13 (di-NHC) 5 Br 2 ] 3+ (di-NHC = PhCH 2 -C 7 H 4 N 2 -(CH 2 ) 3 -C 7 H 4 N 2 -CH 2 Ph) ( Fig. 6c) 88 with an icosahedral Au 13 (8e) core were synthesized. The latter was robust at temperatures (-70°C and 100°C) and under various redox and pH conditions (pH = 1-11) and survived for < 6min even when treated with aqua regia.…”

Section: Improving Robustnessmentioning

confidence: 99%

“…As a result, [Au 13 (NHC Np ) 9 Cl 3 ] 2+ (NHC Np = C 7 H 4 N 2 (CH 2 (2-C 10 H 7 )) 2 ) and [Au 13 (di-NHC) 5 Br 2 ] 3+ exhibit visible photoluminescence with quantum yields as high as 16 and 15 %, respectively. 86,88…”

Section: Improving Robustnessmentioning

confidence: 99%

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Ligand-protected gold/silver superatoms: current status and emerging trends

et al. 2020

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Section: Improving Robustnessmentioning

confidence: 99%

Section: Improving Robustnessmentioning

confidence: 99%

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Ligand-protected gold/silver superatoms: current status and emerging trends

et al. 2020

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“…In the community, NHCs represent a new class of ligands in stabilizing and activating clusters [7] . Examples include Au 11 , [7a] Au 13 , [7b,c] and Au 25 [7d] NCs featuring gold‐carbene interface have been reported. As part of our continuing effort in the study of metal‐carbene interface in metal nanomaterials, it occurred to us that mixed ligands on a metal cluster surface may give rise to novel nanomaterials with unusual properties.…”

Section: Introductionmentioning

confidence: 99%

Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity

Shen

Hazer

et al. 2020

Angewandte Chemie

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Deciphering the molecular pictures of the multi‐component and non‐periodic organic‐inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles can be precisely quantified through comprehensive characterization of a novel gold cluster, Au44(iPr2‐bimy)9(PA)6Br8 (1), which features three types of ligands, namely, carbene (1,3‐diisopropylbenzimidazolin‐2‐ylidene, iPr2‐bimy), alkynyl (phenylacetylide, PA), and halide (Br), respectively. The delicately balanced stereochemical effects and bonding capabilities of the three ligands give rise to peculiar geometrical and electronic structures. Remarkably, despite its complex and highly distorted surface structure, cluster 1 exhibits unusual catalytic properties and yet it is highly stable, both chemically and thermally. Moreover, rich reactive sites on the cluster surface raise the prospect of bio‐compatibility (as it can be functionalized to yield water‐soluble derivatives) and bio‐applications.

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“…In recent reports, this class of ligands were successfully introduced in clusters [22]. Several works on gold NCs, such as Au3 [25,26], Au11 [27], Au13 [28,29], Au25 [30], and Au44 [31], demonstrated that NHCs could endow them with exciting stability, luminescence and reactivity. NHC-stabilized Ag and Cu clusters have also been prepared, in which no hydride was observed [32][33][34][35][36][37].…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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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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Superatomic Au13 clusters ligated by different N-heterocyclic carbenes and their ligand-dependent catalysis, photoluminescence, and proton sensitivity

Cited by 93 publications

References 30 publications

Ligand-protected gold/silver superatoms: current status and emerging trends

Ligand-protected gold/silver superatoms: current status and emerging trends

Surface Coordination of Multiple Ligands Endows N‐Heterocyclic Carbene‐Stabilized Gold Nanoclusters with High Robustness and Surface Reactivity

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

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