Thermal Stability and Electronic Properties of N-Heterocyclic Carbene-Protected Au<sub>13</sub> Nanocluster and Phosphine-Protected Analogues

Chen, Zhimin; Sun, Fang; Tang, Qing

doi:10.1021/acs.jpclett.3c02965

Cited by 3 publications

(1 citation statement)

References 47 publications

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“…Only small amounts of decomposition were observed after 24 h, which is similar to what is reported for clusters stabilized by monotopic NHCs . Although exactly analogous phosphine-stabilized clusters are not known and the stability of known phosphine-stabilized clusters at elevated temperatures is not often reported, ,,− related [Au 11 (PPh 3 ) 8 Cl 2 ]Cl decomposes after 3–4 h at 70 °C in solution. , …”

Section: Resultssupporting

confidence: 76%

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Albright,

Malola,

Jacob

et al. 2024

Chem. Mater.

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A series of chiral Au 13 nanoclusters were synthesized via the direct reduction of chiral dinuclear Au(I) halide complexes ligated by chiral dioxalone-linked bis-N-heterocyclic carbene (bisNHC) ligands. Electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory (DFT) calculations confirmed the molecular formula to be [Au 13 (bisNHC) 4 I 4 ] + , with a chiral arrangement of the four ditopic NHC ligands around the icosahedral Au 13 core. Circular dichroism (CD) spectroscopy of the two enantiomers of the Au 13 clusters shows distinct mirror images of the enantiomers and supports chirality transfer from ligands to the metal core. A plausible model structure was built with the assistance of theoretical analysis, and DFT calculations were employed to explain the origin of the optical and CD activities and their dependence on the binding arrangement of the ditopic bisNHC ligands. The clusters show remarkable stability with minimal decomposition in various solutions both at elevated and room temperatures. The potential of these clusters as nanocatalysts in the electrocatalytic reduction of CO 2 to CO is described.

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Section: Resultssupporting

confidence: 76%

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Albright,

Malola,

Jacob

et al. 2024

Chem. Mater.

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Relationship between Structural Defects and Free Electrons in Icosahedral Nanoclusters

Feng,

Lv,

Wei

et al. 2024

J. Phys. Chem. Lett.

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According to the classic superatom model, metal nanoclusters with a "magic number" of free valence electrons display high stability, manifesting as the closed-shell-dependent electronic robustness. The icosahedral nanobuilding blocks containing eight free electrons were the most common in constructing metal nanoclusters; however, the structure defect-dependent variations of the free electron count in icosahedral configurations are still far from thorough research. Here, we reported a hydride-containing [Pt 2 Ag 15 (SAdm) 4 (DPPOE) 4 H] 2+ nanocluster with two largely defective Pt 1 Ag 8 icosahedral cores. Together with previously reported complete or slightly defective icosahedra in metal nanoclusters, the largely defective Pt 1 Ag 8 core provided important clues to reveal the evolutionary mode of structural defects and free electrons in icosahedral nanoclusters; the free electron count of icosahedron was reduced two-by-two (i.e., from 8e to 6e and then to 4e) accompanied by the structure defection. Overall, the work presented a novel Pt 2 Ag 15 nanocluster with a largely defective core structure that enables an atomic-level understanding of the relationship between structural defects and free electrons in icosahedral nanoclusters.

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Revisiting the activity origin of the PtAu₂₄(SR)₁₈ nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique

Sun,

Qin,

Tang

et al. 2024

Chem. Sci.

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Thermal Stability and Electronic Properties of N-Heterocyclic Carbene-Protected Au₁₃ Nanocluster and Phosphine-Protected Analogues

Cited by 3 publications

References 47 publications

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Relationship between Structural Defects and Free Electrons in Icosahedral Nanoclusters

Revisiting the activity origin of the PtAu₂₄(SR)₁₈ nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique

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Thermal Stability and Electronic Properties of N-Heterocyclic Carbene-Protected Au13 Nanocluster and Phosphine-Protected Analogues

Cited by 3 publications

References 47 publications

Enantiopure Chiral Au13 Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO2

Enantiopure Chiral Au13 Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO2

Relationship between Structural Defects and Free Electrons in Icosahedral Nanoclusters

Revisiting the activity origin of the PtAu24(SR)18 nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique

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Thermal Stability and Electronic Properties of N-Heterocyclic Carbene-Protected Au₁₃ Nanocluster and Phosphine-Protected Analogues

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Enantiopure Chiral Au₁₃ Nanoclusters Stabilized by Ditopic N-Heterocyclic Carbenes: Synthesis, Characterization, and Electrocatalytic Reduction of CO₂

Revisiting the activity origin of the PtAu₂₄(SR)₁₈ nanocluster for enhanced electrocatalytic hydrogen evolution by combining first-principles simulations with the experimental in situ FTIR technique