Atomically Precise Copper Nanoclusters

Dong, Chunwei; Nematulloev, Saidkhodzha; Yuan, Peng; Bakr, Osman M.

doi:10.1002/9781119788676.ch8

Cited by 2 publications

(2 citation statements)

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“…8,9 In this context, atomically precise nanoclusters (APNCs) have offered significant promise for delivery of earth-abundant catalyst systems with atomistic control. [10][11][12] APNCs capture the essential features of bulk metal chalcogenide catalysts including their highly delocalized electronic structures and flexible configuration of multimetallic sulfide active sites, both of which contribute to lowering activation energy barriers through cooperative multimetallic pathways. [13][14][15][16][17][18][19][20][21][22][23][24][25] Additionally, their discrete, atomically precise structures confer some distinct advantages.…”

Section: Introductionmentioning

confidence: 99%

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Trenerry,

Bailey

2024

Preprint

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Atomically precise copper chalcogenide nanoclusters are an exceptionally diverse class of nanomaterials with potential applications in chemiluminescence, sensing, and catalysis. However, most previously reported nanoclusters have been characterized exclusively in the solid state, leaving open questions as to their stability and function in solution. In this work, we report the first detailed solution-phase investigation of speciation, electrochemistry, and decomposition of atomically precise [Cu12S6] supported by a series of mono- and ditopic alkyldiphenylphosphines PPh2R (R = Et, -(CH2)5-, -(CH2)8-). While electronically identical, this series of ligands features monotopic and ditopic binding modes spanning zero, one, or three axes of the [Cu12S6] core, facilitating an in-depth examination of the impact of phosphine binding topology on solution behaviour. We find that binding topology dictates the extent of speciation, with complete solution stability being afforded through use of the longer octane chelate dppo (1,8-bis(diphenylphosphino)octane). Thus, the 1H and DOSY NMR spectra of [Cu12S6(dppo)4] indicate a rigid, stereochemically locked ligand configuration in which substantial stabilizing CH---S interactions are present. Meanwhile, electrochemical analysis coupled with DFT calculations indicates that the [Cu12S6] core undergoes a quasireversible one-electron oxidation at –0.50 V vs Fc0/+. In contrast, prolonged air exposure or treatment with chemical oxidants results in cluster degradation with formation of phosphine sulfide byproducts. This work demonstrates both progress and challenges in controlling the solution-phase behaviour and redox chemistry of phosphine-supported copper chalcogenide nanoclusters.

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Section: Introductionmentioning

confidence: 99%

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Trenerry,

Bailey

2024

Preprint

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“…28,29 Specifically, the luminescence mechanism of copper clusters finds elucidation through diverse charge transfer pathways. 30,31 However, it is not yet completely clear for silver clusters. The luminescence is affected by both internal factors (metal core and ligands) and external factors (solvent, temperature, etc.).…”

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confidence: 99%

Incorporation of the ⁹⁹TcO₄^– Anion within the Ag₂₄(C≡C^tBu)₂₀⁴⁺ Cluster Unveiling the Unique Shell-to-Core Charge Transfer

Tao,

Luan,

Yang

et al. 2024

J. Am. Chem. Soc.

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We present the first example of an 99 TcO 4 − anion entrapped within the cavity of a silver cluster, revealing an unprecedented photoinduced charge transfer phenomenon. [Ag 24 (C�C t Bu) 20 ( 99 TcO 4 )]•(BF 4 ) 3 (denoted as 99 TcO 4 − @Ag 24 ) was successfully synthesized and structurally characterized. Single-crystal X-ray diffraction and Raman spectroscopy reveal that the tetrahedral structure of the 99 TcO 4 − anion sustains significant symmetry breaking with weakened Tc−O bond strength under confinement within the Ag 24 (C�C t Bu) 20 4+ cluster. Notably, 99 TcO 4 − @Ag 24 exhibits a broadband electronic absorption spectrum in the visible region, which was absent for the other 99 TcO 4 − -containing compounds. Density functional theory calculations elucidate that host−guest electrostatic interactions result in an electron polarization effect between the 99 TcO 4 − anion core and the Ag 24 cationic shell. The emergence of an absorption band in 99 TcO 4 − @Ag 24 is rationalized by intermolecular charge transfer from the Ag 24 electronic states to the lowest unoccupied molecular orbitals of 99 TcO 4 − instead of the intramolecular electron transition observed in other 99 TcO 4 − -containing compounds.

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Atomically Precise Copper Nanoclusters

Cited by 2 publications

References 97 publications

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Incorporation of the ⁹⁹TcO₄^– Anion within the Ag₂₄(C≡C^tBu)₂₀⁴⁺ Cluster Unveiling the Unique Shell-to-Core Charge Transfer

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Atomically Precise Copper Nanoclusters

Cited by 2 publications

References 97 publications

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Ditopic ligand effects on solution-phase equilibria and electrochemistry of atomically precise copper chalcogenide nanoclusters

Incorporation of the 99TcO4– Anion within the Ag24(C≡CtBu)204+ Cluster Unveiling the Unique Shell-to-Core Charge Transfer

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Incorporation of the ⁹⁹TcO₄^– Anion within the Ag₂₄(C≡C^tBu)₂₀⁴⁺ Cluster Unveiling the Unique Shell-to-Core Charge Transfer