Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Wang, Endong; Xu, Wen; Zhu, Bi; Gao, Yi

doi:10.1002/smll.202001836

Cited by 24 publications

(21 citation statements)

References 52 publications

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“…Moreover, the protecting Au 48 S 20 (PH 3 ) 12 layer exhibits four novel Au 4 S 4 motifs, which adds to the libraries of different staple motifs usually found in ligand-protected gold clusters. [70][71][72][73] Such motifs are located in an almost perfect tetrahedral fashion with angles of ~110°, providing a prototypical environment to support and evaluate tentative tetrahedral cluster-cores (109.5°for a perfect tetrahedron). This encourages the search for further examples of SP 3 -cluster nodes waiting to be discovered featuring larger aggregates and leaving the question if larger electron counts, as 32-ce cores, are able to exhibit a tetrahedral shape.…”

Section: Resultsmentioning

confidence: 99%

Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Muñoz-Castro

2021

Zeitschrift anorg allge chemie

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Dedicated to Professor Hansgeorg Schnöckel on the occasion of his 80th birthdayLigand-protected gold clusters are usually understood in terms of the superatom concept, where certain species are able to behaves as prototypical molecules. Here, we discuss the metalloid cluster Au 70 S 20 (PPh 3 ) 12 in terms of the bonding characteristics of its inner 18-cluster electron Au 22 4 + core. Our interpretation is based on a SP 3 -hybridized core involving four fused Au 6 units denoting four equivalent hybridized localized orbitals, with the remaining electrons from the 1D 10 state remaining as formally non-bonding orbitals. Such characteristics expose a rationalization of Au 70 S 20 (PPh 3 ) 1 as a superatomic analog for a transition metal complex, following the 18-electron rule, mimicking the classical bonding picture of the tetrahedral Ni(CO) 4 complex. The Au 22 core as an aggregate of Au 6 units encourages the search for further examples of SP 3 -cluster nodes precluding larger aggregates, contributing to the design opportunities of functional clusters and nanoparticles.

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Section: Resultsmentioning

confidence: 99%

Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Muñoz-Castro

2021

Zeitschrift anorg allge chemie

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“…Finally, according to the steric hindrance caused by the benzene ring and methyl group, we adjusted the orientation of ligands to prevent overdense packing. The previous studies on small-sized thiolate-protected gold clusters − were also employed for reference. All the structures were optimized by density functional theory method, as implemented in Gaussian 09 program package .…”

Section: Methodsmentioning

confidence: 99%

Effect of Ligand Structures on Ligand-Protected Gold Clusters: [Au–(p-/m-/o-MBT)]_1–8 Clusters

et al. 2022

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The controllable preparation of ligand-protected clusters is still an unresolved problem, which may be due to that their formation mechanism is unclear. We propose that the ligand is the key to solve the above problems. Here, by using p-, m-, and o-methylbenzenethiol ligand protected gold clusters as examples, we try to explore the effect of ligand structures on ligand-protected gold clusters. The geometrical structures, relative stabilities and surface properties of small-sized ligand-protected gold clusters [Au−SR] 1−8 (SR = p-/m-/o-MBT) have been systematically studied based on the density functional theory. The results show that the ground state structures of [Au−SR] 1−8 clusters tend to form closed rings except for [Au−SR] 1,2 . The different structures of ligand have significant effect on the structures and stabilities of ligand-protected clusters. By analyzing their surface properties and possible growth patterns, it is found that [Au−SR] 1,2 clusters serve as the basic building blocks, and the larger clusters can be regarded as the combinations of them. This study provides some insights into the effect of ligands on ligand-protected clusters, which is useful for understanding the formation mechanism of ligandprotected clusters.

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“…There are numbers of experimental and theoretical studies on the catalytic activity of atomically precise thiolate‐protected gold clusters due to their molecular, strongly size‐dependent behavior, stability, and tunability of properties. [ 22‐23 ] Au 25 represents one of the brightest molecular stars in thiolate‐protected gold nanocluster field. [ 24‐25 ] Two typical Au 25 clusters have been studied in detail so far, they are Nanorod‐type Au 25 ‐bi (biicosahedral‐structure Au 25 (PPh 3 ) 10 (SR) 5 X 2 ) and nanosphere‐type Au 25 ‐i (icosahedral core‐shell‐structure Au 25 (SR) 18 ).…”

Section: Background and Originality Contentmentioning

confidence: 99%

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

Xue

Wei

et al. 2022

Chin. J. Chem.

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Ultrasmall atomically precise thiolate-protected gold nanoclusters with surface open sites are crucial for practical applications in catalysis. However, there is a lack of systematic studies that unify the kernels-isomerization, modification of peripheral ligands and electronic effects into one system, as well as their correlation to catalytic performances. In this work, three structurally related Au 25 nanoclusters with reported star Au 25 kernels, Au 25 -i-FTP, Au 25 -bi-FTP, and Au 25 -bi-CHT have been synthesized through two different methods: one-pot direct reduction and two-step reduction by using AsPh 3 as converter. Their structures and catalytic performance have been comparatively investigated. Au 25 -i-FTP has a classic Au 13 core capped by six dimeric RS-Au-SR-Au-SRs, while Au 25 -bi-FTP and Au 25 -bi-CHT feature typical rod-shaped biicosahedral geometric kernel. All of the three Au 25 clusters were effective catalysts for oxidation of organosilanes, different from conclusions obtained in literature. Especially, the nanorod-type Au 25 -bi-CHT clusters protected by flexible thiol ligands showed very good catalytic performance in this reaction, the conversion and selectivity were close to 100% within 5 min. The ligand rigidity and electron effects work together to modulate the catalytic properties. The findings inspire us to rethink kernel and ligand effects on catalytic property, and the principle demonstrated here will possibly be widely-used in high active atom-precise catalysts modification.

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Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Cited by 24 publications

References 52 publications

Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Effect of Ligand Structures on Ligand-Protected Gold Clusters: [Au–(p-/m-/o-MBT)]_1–8 Clusters

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

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Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Cited by 24 publications

References 52 publications

Au70S20(PPh3)12 as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Au70S20(PPh3)12 as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Effect of Ligand Structures on Ligand-Protected Gold Clusters: [Au–(p-/m-/o-MBT)]1–8 Clusters

Kernels‐Different Au25Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects

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Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Au₇₀S₂₀(PPh₃)₁₂ as Superatomic Analog to 18‐electron Transition‐Metal Complexes

Effect of Ligand Structures on Ligand-Protected Gold Clusters: [Au–(p-/m-/o-MBT)]_1–8 Clusters

Kernels‐Different Au₂₅Nanoclusters Enhanced Catalytic Performance via Modification of Ligand and Electronic Effects