Mechanistic insights into Ag+induced size-growth from [Au6(DPPP)4]2+to [Au7(DPPP)4]2+clusters

Lv, Ying; Wu, Xiaohang; He, Shuping; Yu, Haizhu

doi:10.1039/d2na00301e

Cited by 2 publications

(2 citation statements)

References 60 publications

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“…254 According to SCXRD analysis, [Au 6 (dppp) 4 ] 2+ comprises a bi-capped tetrahedral skeleton (tetrahedron + exo), while [Au 7 (dppp) 4 ] 3+ had an edge-bridged bitetrahedral geometry and one exo gold atom (bitetrahedron + exo). In view of this transformation process, Yu and coworkers proposed a plausible mechanism combined with DFT calculations 286 (Figure 30). The structural transformation starts with the successive doping of the Ag(I) ion, which activates the terminal Au atoms and generates the [Au] + source for subsequent conversion.…”

Section: Metal Source Induced Doping and Tailoringmentioning

confidence: 99%

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Chemical Flexibility of Atomically Precise Metal Clusters

Li,

Dong

et al. 2024

Chem. Rev.

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Ligand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with an organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging chemical flexibility to expand the library of available materials and stimulate the development of new functionalities is becoming an increasingly pressing requirement. This Review focuses on the origin of chemical flexibility from the structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments interactions, metal-to-ligand ratios, and thermodynamic effects. In the introduction, we briefly outline the development of metal clusters and explain the differences and commonalities of M(I)/M(I/ 0) coinage metal clusters. Additionally, we distinguish the bonding characteristics of metal atoms in the inorganic core, which give rise to their distinct chemical flexibility. Section 2 delves into the structural analysis, bonding categories, and thermodynamic theories related to metal clusters. In the following sections 3 to 7, we primarily elucidate the mechanisms that trigger chemical flexibility, the dynamic processes in transformation, the resultant alterations in structure, and the ensuing modifications in physical−chemical properties. Section 8 presents the notable applications that have emerged from utilizing metal clusters and their assemblies. Finally, in section 9, we discuss future challenges and opportunities within this area.

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Section: Metal Source Induced Doping and Tailoringmentioning

confidence: 99%

Section: Chemical Inducements-triggered Reactionsmentioning

confidence: 99%

Chemical Flexibility of Atomically Precise Metal Clusters

Li,

Dong

et al. 2024

Chem. Rev.

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Conversion mechanism of the atomically precise group IB metal nanoclusters by theoretical calculations

Lv,

Nie,

et al. 2024

Chemical Physics Reviews

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The controllable synthesis and design of group IB metal (i.e., Au/Ag/Cu) and their alloy nanoclusters (IB-NCs) rely on an elucidation of the conversion mechanism, bonding preference, and structure–property relationships. In the past decades, the development of cluster-to-cluster transformation and spectroscopic tracking strategy have provided important mechanistic insights that greatly help researchers improve synthetic skills and explore the application of IB-NCs. Specifically, with the aid of DFT calculations, the structural information of cluster-to-cluster conversion, including the intermediates and active sites, can be deduced from the atomic level. In this review, the conversion mechanisms of IB-NCs in the past three years have been reviewed to summarize the key factors influencing structural transformation and reactivity. The three types of cluster-to-cluster conversion (i.e., foreign metal source, foreign ligand, and other reagents/condition-induced conversion) were highlighted for further synthesis and design of functional nanoclusters.

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Mechanistic insights into Ag⁺induced size-growth from [Au₆(DPPP)₄]²⁺to [Au₇(DPPP)₄]²⁺clusters

Abstract: The size-conversion of atomically precise metal nanoclusters lies the foundation to elucidate the inherent structure-activity correlations at the nanometer scale. Herein, the mechanism of the Ag+-induced size-growth from [Au6(dppp)4]2+ to...

Cited by 2 publications

References 60 publications

Chemical Flexibility of Atomically Precise Metal Clusters

Chemical Flexibility of Atomically Precise Metal Clusters

Conversion mechanism of the atomically precise group IB metal nanoclusters by theoretical calculations

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