Isomerism in Au<sub>28</sub>(SR)<sub>20</sub> Nanocluster and Stable Structures

Chen, Yuxiang; Liu, Chong; Tang, Qing; Zeng, Chenjie; Higaki, Tatsuya; Das, Anindita; Jiang, De‐en; Rosi, Nathaniel L.; Jin, Rongchao

doi:10.1021/jacs.5b12094

Cited by 252 publications

(322 citation statements)

References 40 publications

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“…A grand challenge to scientists in this field, however, is the precise determination of atomic structures of liganded gold clusters. To date, atomic structures of tens of liganded gold clusters have been determined via X-ray crystallography56789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263. Nevertheless, these revelations appear serendipitous as the structural determination largely hinges on availability of single crystals for the liganded gold clusters.…”

mentioning

confidence: 99%

A grand unified model for liganded gold clusters

et al. 2016

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A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours' (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

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mentioning

confidence: 99%

A grand unified model for liganded gold clusters

et al. 2016

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“…On the other hand, that with bulky ligands, such as t Bu-PhSH, often causes the structural transformation. 5,30 At the present, a clear rule has not been established for the final fate of the deformed cluster. The final fate of the deformed cluster (quasi-isomerization or size transformation) seems to be determined by the magnitude of structural transformation, and the existence or nonexistence of isomer structures with similar stability in the subjected cluster.…”

Section: Ligand Exchangementioning

confidence: 79%

“…18 Knowledge of intercluster metal exchange has drastically improved recently. For example, Pradeep et al 38 (SPhF) 30 ] 4 as a precursor, metal exchange occurs while maintaining the number of metal atoms and ligands ( Fig. 6(a)) as in the case of the other two reactions considered (Figs.…”

Section: Metal Exchangementioning

confidence: 99%

“…Currently, this phenomenon has not been proven experimentally for Au 24 (SR) 20 . However, in 2016, Jin et al 30 reported that when the ligands of Au 28 (SPh-t Bu) 20 (SPh-t Bu = 4-tert-butylbenzenethiolate) were exchanged with 1-cyclohexanethiolate (S-c-C 6 H 11 ), the skeletal structure of the cluster was altered ( Fig. 3(a)).…”

Section: Ligand Exchangementioning

confidence: 99%

“…The final fate of the deformed cluster (quasi-isomerization or size transformation) seems to be determined by the magnitude of structural transformation, and the existence or nonexistence of isomer structures with similar stability in the subjected cluster. 5,30 …”

Section: Ligand Exchangementioning

confidence: 99%

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Perspective: Exchange reactions in thiolate-protected metal clusters

et al. 2017

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Thiolate-protected metal clusters can exchange ligands or metal atoms with other substances such as coexisting ligands, complexes, and metal clusters in solution. Using these reactions, it is possible to synthesize metal clusters with new physical and chemical properties. Although the occurrence of such reactions was recognized nearly 20 years ago, their details were not well understood. In recent years, techniques for the precise synthesis of metal clusters and their characterization have progressed considerably and, as a result, details of these reactions have been clarified. In this perspective, we focus on the most-studied thiolate-protected gold clusters and provide a summary of recent findings as well as future expectations concerning the exchange reactions of these clusters.

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