A revisit to the structure of Au20(SCH2CH2Ph)16: a cubic nanocrystal-like gold kernel

Wang, Pu; Sun, Xiang-Xiang; Liu, Xia; Xiong, Lin; Ma, Zhongyun; Wang, Yong; Pei, Yong

doi:10.1039/c8nr00995c

Cited by 10 publications

(10 citation statements)

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“…The mechanism involves two steps: first an exterior Au(0) atom is inserted between a pair of neighboring SR groups in the ligand shell, and then the resulting μ 4 -SR group leaves to form a new Au 3 triangle unit. As shown in Figure , the structural evolution from 8e Au 28 (SR) 20 (R = C 6 H 11 ) to 12e Au 30 (SR) 18 (R = t -Bu) as well as the recently reported Au 20 (SR) 16 isomeric nanocrystal structure all can be explained from this mechanism. Recently, from the ligand exchange reaction of the Ag 3 @Au 15 (SR) 13 cluster, we succeeded in the synthesis and determination of the cluster structure of a Ag@Au 16 (SR) 13 alloy cluster.…”

Section: Structural Evolution Of Fcc-type Clusterssupporting

confidence: 59%

Growth-Rule-Guided Structural Exploration of Thiolate-Protected Gold Nanoclusters

et al. 2018

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CONSPECTUS: Understanding the structure and structure−property relationship of atomic and ligated clusters is one of the central research tasks in the field of cluster research. In chemistry, empirical rules such as the polyhedral skeleton electron pair theory (PSEPT) approach had been outlined to account for skeleton structures of many main-group atomic and ligandprotected transition metal clusters. Nonetheless, because of the diversity of cluster structures and compositions, no uniform structural and electronic rule is available for various cluster compounds. Exploring new cluster structures and their evolution is a hot topic in the field of cluster research for both experiment and theory. In this Account, we introduce our recent progress in the theoretical exploration of structures and evolution patterns of a class of atomically precise thiolate-protected gold nanoclusters using density functional theory computations. Unlike the conventional ligand-protected transition metal compounds, the thiolate-protected gold clusters demonstrate novel metal core/ligand shell interfacial structures in which the Au m (SR) n clusters can be divided into an ordered Au(0) core and a group of oligomeric SR[Au(SR)] x (x = 0, 1, 2, 3, ...) protection motifs. Guided by this "inherent structure rule", we have devised theoretical methods to rapidly explore cluster structures that do not necessarily require laborious global potential energy surface searches. The structural predictions of Au 38 (SR) 24 , Au 24 (SR) 20 , and Au 44 (SR) 28 nanoclusters were completely or partially verified by the later X-ray crystallography studies. On the basis of the analysis of cluster structures determined by X-ray crystallography and theoretical prediction, a structural evolution diagram for the face-centered-cubic (fcc)type Au m (SR) n clusters with m up to 92 has been preliminarily established. The structural evolution diagram indicates some basic structural and electronic evolution patterns of thiolate-protected gold nanoclusters. The fcc Au m (SR) n clusters show a genetic structural evolution pattern in which each step of cluster size increase results in the formation of another Au 4 tetrahedron or Au 3 triangle unit in the Au core, and every increase of a structural unit in the Au core leads to an increase of two electrons in the whole cluster. The unique one-or two-dimensional cluster size evolution, the isomerism of the Au−S framework, and the formation of a double-helical and cyclic tetrahedron network in the fcc Au m (SR) n clusters all can be addressed from this evolution pattern. The summarized cluster structural evolution diagrams enable us to further explore more stable cluster structures and understand their structure−electronic structure−property relationships.

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Section: Structural Evolution Of Fcc-type Clusterssupporting

confidence: 59%

Growth-Rule-Guided Structural Exploration of Thiolate-Protected Gold Nanoclusters

et al. 2018

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“…Since its conception, others have utilized the theory to test the stability of Au NC isomers. 18,19 However, more work is still needed to expand the model's reach, namely the analysis of Au NCs in different size regimes. In addition, using this theory in concert with other developed structure-property relationships on Au NCs could potentially generate a very effective predictive tool bridging the structure with the stability and properties of Au NCs.…”

Section: Introductionmentioning

confidence: 99%

Structure–property relationships on thiolate-protected gold nanoclusters

Cowan

Mpourmpakis

2019

Nanoscale Adv.

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“…Investigation on the structural transformation via ligand exchange is rapidly progressing, as it can unveil the fundamental understanding of the structural transformation at the atomic level. − Specific size/structure of the kernel determined by different ligands during the ligand exchange is puzzling due to the dependency on various parameters such as steric, electronic, and aromatic properties of ligands . Even though bulkiness of the ligand plays a vital role in size/structure specificity, we cannot rule out the influence of other parameters such as aromaticity and electronic effects of the ligands, as demonstrated in various stable structures with thiolated benzene and 2-phenylethanethiol. − For example, when [Au 144 (PET) 60 ] (PET stands for 2-phenylethanethiol) was transformed to [Au 133 (TBBT) 52 ] (TBBT stands for tert -butylbenzenethiol) via TBBT ligand exchange, aromaticity was considered to cause interligand interaction, while steric repulsion was considered to be triggering the core conversion .…”

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Synergistic Effect of Bridging Thiolate and Hub Atoms for the Aromaticity Driven Symmetry Breaking in Atomically Precise Gold Nanocluster

Maman

Nair

Nazeeja

et al. 2020

J. Phys. Chem. Lett.

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The symmetry of atomically precise nanoclusters is influenced by the specific geometry of the kernel and the arrangement of staple motifs. To understanding the role of ligand and its effect on the breaking of symmetry during ligand exchange transformation, it is necessary to have a mechanism of transformation in an atomically precise manner. Herein, we report the structural transformation from bipyramidal kernel to icosahedral kernel via ligand exchange. The transformation of [Au23(CHT)16]− to [Au25(2-NPT)18]− through ligand (aromatic) exchange revealed two important principles. First, the combined effort of experimental and theoretical study on structural analysis elucidated the mechanism of this structural transformation where “bridging thiolate” and “hub” gold atoms play a crucial role. Second, we have found that the higher crystal symmetry of the Au23 cluster is broken to lower crystal symmetry during the ligand exchange process. This showed that during ligand exchange, the hub atoms and μ3-S atoms get distorted and contributed to the ligand-staple motif formation. These phenomena specified that the ligand effects might be the pivotal factor to impose lower symmetry of the crystal system in the product clusters.

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A revisit to the structure of Au₂₀(SCH₂CH₂Ph)₁₆: a cubic nanocrystal-like gold kernel

Cited by 10 publications

References 57 publications

Growth-Rule-Guided Structural Exploration of Thiolate-Protected Gold Nanoclusters

Growth-Rule-Guided Structural Exploration of Thiolate-Protected Gold Nanoclusters

Structure–property relationships on thiolate-protected gold nanoclusters

Synergistic Effect of Bridging Thiolate and Hub Atoms for the Aromaticity Driven Symmetry Breaking in Atomically Precise Gold Nanocluster

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