The one/two atom size-reduction of [Au23SCy16]−induced by the [Au6(dppp)4]2+cluster

Zhang, Lichao; Fan, Daoqing; Shi, Yanan; He, Shuping; Cui, Mengting; Yu, Haizhu; Zhu, Manzhou

doi:10.1039/d3ra01606d

Cited by 2 publications

(1 citation statement)

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“…In this scenario, the different reaction modes and reaction sites were all examined in this study. The Au−S bond dissociation energy (BDE) values, which correlate directly with the possibility of Path I-a, have been provided in an early study of our group 46 and are provided in Table S1 for earlier studies, 18 we first examined the energy demands for the ligand exchange on S 1 and S 4 sites (i.e., the Au−S bond at the core−shell interference of the Au 3 S 4 motif). From Figure 3a, the relative energies of the H-transfer transition state from complexes Int1 (1−1−2) and Int1 (5−4−4) are 15.4 and 19.3 kcal/ mol.…”

Section: ■ Introductionmentioning

confidence: 99%

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Shi,

Lv,

Wang

et al. 2023

J. Phys. Chem. A

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Ligand exchange has been widely used to synthesize novel thiolated gold nanoclusters and to regulate their specific properties. Herein, density functional theory (DFT) calculations were conducted to investigate the kinetic profiles of the ligand exchange of the [Au23(SCy)16]− nanocluster with an aromatic thiolate (2-napthalenethiol). The three types of staple motifs (i.e., trimetallic Au3S4, monometallic AuS2, and the bridging thiolates) of the Au23 cluster precursor could be categorized into eight groups of S sites with different chemical environments. The ligand exchange of all of them occurs favorably via the SN1-like pathway, with one site starting with the Au–S dissociation and seven other sites starting with the H-transfer steps. By contrast, the SN2-like pathway (i.e., the synergistic SCy-to-SAr exchange prior to the H-transfer step) is unlikely in the target systems. Meanwhile, the Au–S bond on the capping Au atom of the bicapped icosahedral Au15 core is the most active one, while the S sites on Au3S4 (except for the one remote from the metallic core) are all competitive exchanging sites. The ligand exchange activity of the bridging thiolate and the remote S site on Au3S4 is significantly less reactive. The calculation results correlate with the multiple ligand exchange within only a few minutes and the preferential etching of the AuS2 staple with the foreign ligands reported in earlier experiments. The relative activity of different staples might be helpful in elucidating the inherent principles in the ligand exchange-induced size-evolution of metal nanoclusters.

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Section: ■ Introductionmentioning

confidence: 99%

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Shi,

Lv,

Wang

et al. 2023

J. Phys. Chem. A

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Impact of the Peripheral Ligand Layer on the Excited-State Deactivation Mechanism of Au₃₈S₂(S-Adm)₂₀ and Au₃₀(S-Adm)₁₈ (S-Adm = Adamantanethiolate) Clusters

Li,

Wang,

Pei

2024

J. Phys. Chem. Lett.

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Gold nanoclusters are ideal fluorescent labels for biological imaging, disease diagnosis, and treatment. Understanding the origin of the photoluminescence phenomenon in ligand-protected gold nanoclusters is crucial for both basic science and practical applications. In this study, density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed to study the mechanism of excited state deactivation of Au38S2(S-Adm)20 and Au30(S-Adm)18 (S-Adm = adamantanethiolate) clusters, which have similar sizes and compositions. The computational results indicate that the differences in structural symmetry and peripheral ligand layer lead to quite different excited state deactivation mechanisms and excited state lifetimes in Au38S2(S-Adm)20 and Au30(S-Adm)18. Specifically, the μ3-S atoms and bridging thiolate (SR) in the ligand layer of Au38S2(S-Adm)20 significantly suppress the structural relaxation of ligand motifs, resulting in a prolonged excited state lifetime and higher quantum yield. For the Au30(S-Adm)18, due to the symmetry forbidden and large structural relaxation of the ligand shell, a rapid nonradiative transition process resulted. This study provides new insights into how the photoluminescence of ligand-protected gold nanoclusters is influenced by their structure and symmetry.

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The one/two atom size-reduction of [Au₂₃SCy₁₆]⁻induced by the [Au₆(dppp)₄]²⁺cluster

Abstract: [Au22SCy14(dppp)]2+ and [Au21SCy12(dppp)2]+ clusters were formed as the dominant products in the equimolar inter-cluster reaction of [Au23SCy16]− and [Au6(dppp)4]2+. The active etching sites of the Au23 precursor lie in AuS2 motifs.

Cited by 2 publications

References 40 publications

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Impact of the Peripheral Ligand Layer on the Excited-State Deactivation Mechanism of Au₃₈S₂(S-Adm)₂₀ and Au₃₀(S-Adm)₁₈ (S-Adm = Adamantanethiolate) Clusters

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The one/two atom size-reduction of [Au23SCy16]−induced by the [Au6(dppp)4]2+cluster

Abstract: [Au22SCy14(dppp)]2+ and [Au21SCy12(dppp)2]+ clusters were formed as the dominant products in the equimolar inter-cluster reaction of [Au23SCy16]− and [Au6(dppp)4]2+. The active etching sites of the Au23 precursor lie in AuS2 motifs.

Cited by 2 publications

References 40 publications

Activity of Different AunSn+1 Staples in the Ligand Exchange of Au23(SR)16– with a Single Foreign Thiolate Ligand

Activity of Different AunSn+1 Staples in the Ligand Exchange of Au23(SR)16– with a Single Foreign Thiolate Ligand

Impact of the Peripheral Ligand Layer on the Excited-State Deactivation Mechanism of Au38S2(S-Adm)20 and Au30(S-Adm)18 (S-Adm = Adamantanethiolate) Clusters

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The one/two atom size-reduction of [Au₂₃SCy₁₆]⁻induced by the [Au₆(dppp)₄]²⁺cluster

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Activity of Different Au_nS_n+1 Staples in the Ligand Exchange of Au₂₃(SR)₁₆^– with a Single Foreign Thiolate Ligand

Impact of the Peripheral Ligand Layer on the Excited-State Deactivation Mechanism of Au₃₈S₂(S-Adm)₂₀ and Au₃₀(S-Adm)₁₈ (S-Adm = Adamantanethiolate) Clusters