The pivotal alkyne group in the mutual size-conversion of Au9 with Au10 nanoclusters

Wu, Xiaohang; Lv, Ying; Bai, Yuyuan; Yu, Haizhu; Zhu, Manzhou

doi:10.1039/d1dt01586a

Cited by 3 publications

(3 citation statements)

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“…Given the high steric hindrance around Au 5 , the adjacent bare Ag 1 in Dimer-1, and the easiness for 1,2-P migration in cluster systems, [41][42][43] we examined the possibility of a 1,2-P 2 migration from Au 5 to Ag 1 . The kinetic analysis by partial optimization (via gradually shortening the P 2 -Ag 1 bond distance, see Figure S6 for details) demonstrates the gradual bond cleavage of Au 5 -Ag 1 and Au 3 -Ag 2 bonds.…”

Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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

et al. 2022

Nanoscale Adv.

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Section: Please Do Not Adjust Marginsmentioning

confidence: 99%

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

et al. 2022

Nanoscale Adv.

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“…From [Au 6 (dmpp) 4 Cl 2 ] 2+ , the decomposition could be possibly driven by either a Au–Au or a Au–P dissociation (direct Au–P cleavage or 1,2-P transfer − ). According to the calculation results, the Au 1 –P 1 cleavage is thermodynamically less feasible than the 1,2-P 1 transfer step, while even 1,2-P 1 transfer requires a high energy barrier of 20.7 kcal/mol (Figures S6 and S7).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au₆(dppp)₄]²⁺ to [Au₈(dppp)₄Cl₂]²⁺

et al. 2022

Inorg. Chem.

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Oxidation-induced conversion of gold nanoclusters is an important strategy for preparing novel atomically precise clusters and elucidating the kinetic correlations of different clusters. Herein, the oxidation-induced growth from [Au 6 (dppp) 4 ] 2+ to [Au 8 (dppp) 4 Cl 2 ] 2+ (reported by Konishi and co-workers) has been studied by density functional theory calculations. A successive oxidation → Cl − coordination → oxidation → Cl − coordination sequence occurs first to activate the Au 6 structure, resulting in the high Au(core)−Au(corner) bond cleavage activity and the subsequent formation of [Au 2 (dppp) 2 Cl] + and [Au 4 (dppp) 2 Cl] + fragments. Then, the dimerization of two Au 4 fragments and the rearrangement of the diphosphine coordination occur to generate the thermodynamically stable [Au 8 (dppp) 4 Cl 2 ] 2+ products. The proposed mechanism agrees with the experimental outcome for the fast reaction rate and the residual of the Au 2 components. Specifically, a multivariate linear regression analysis indicates the strong correlation of the oxidation potential of Au 6 , Au 8 , Au 23 , and Au 25 clusters with the HOMO energy, the number of Au atoms, and cluster charge state. The main conclusions [e.g., oxidationinduced Au(corner)−Au(core) bond activation, easy 1,2-P transfer steps, etc.] of this study might be widely applicable in improving our understanding of the mechanism of other cluster-conversion reactions.

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“…Au 10 can be converted to Au 9 after reaction with an equivalent amount of BINAP in the CH 2 Cl 2 solution; moreover, Au 10 can be regained by introducing RCCAu to the Au 9 solution (Figure ). The DFT results indicate that the nucleophilic attack of the phosphine ligand on the Au 10 center and electrophilic attack of the Au(I) complex on the Au 9 core dominate the mutual size-conversions between the Au 10 and Au 9 clusters …”

Section: Variable Ligand-induced Reactionsmentioning

confidence: 99%

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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The pivotal alkyne group in the mutual size-conversion of Au9 with Au10 nanoclusters

Abstract: Herein, density functional theory (DFT) calculations were performed to elucidate the mechanism of the reversible single atom size conversion between [Au10(DMPP)4(C6H11C≡C)]3+ and [Au9(DMPP)4]3+ (DMPP is 2,2’-bis-(dimethylphosphino)-1,1’-biphenyl, the simplified, theoretical model...

Cited by 3 publications

References 38 publications

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

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

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au₆(dppp)₄]²⁺ to [Au₈(dppp)₄Cl₂]²⁺

Chemical Flexibility of Atomically Precise Metal Clusters

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The pivotal alkyne group in the mutual size-conversion of Au9 with Au10 nanoclusters

Abstract: Herein, density functional theory (DFT) calculations were performed to elucidate the mechanism of the reversible single atom size conversion between [Au10(DMPP)4(C6H11C≡C)]3+ and [Au9(DMPP)4]3+ (DMPP is 2,2’-bis-(dimethylphosphino)-1,1’-biphenyl, the simplified, theoretical model...

Cited by 3 publications

References 38 publications

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

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

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au6(dppp)4]2+ to [Au8(dppp)4Cl2]2+

Chemical Flexibility of Atomically Precise Metal Clusters

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

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

Mechanistic Insights into Oxidation-Induced Size Conversion of [Au₆(dppp)₄]²⁺ to [Au₈(dppp)₄Cl₂]²⁺