Structural isomerism in gold nanoparticles revealed by X-ray crystallography

Tian, Shubo; Li, Yi‐Zhi; Li, Man‐Bo; Yuan, Jie; Yang, Jinlong; Wu, Zhikun; Jin, Rongchao

doi:10.1038/ncomms9667

Cited by 271 publications

(326 citation statements)

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“…After proceeding overnight at 100 °C under nitrogen atmosphere, the reaction was terminated by the addition of plenty of methanol. The crude product was thoroughly washed with petroleum ether and methanol for four times, then subjected to subsequent separation and purification by preparative thin-layer chromatography (PTLC)19. Single crystals of the purified nanoclusters were grown by the vapour diffusion of acetonitrile into the toluene solution of the purified nanoclusters at 5 °C.…”

Section: Resultsmentioning

confidence: 99%

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The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

et al. 2017

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Metal nanoclusters have recently attracted extensive interest not only for fundamental scientific research, but also for practical applications. For fundamental scientific research, it is of major importance to explore the internal structure and crystallographic arrangement. Herein, we synthesize a gold nanocluster whose composition is determined to be Au60S6(SCH2Ph)36 by using electrospray ionization mass spectrometry and single crystal X-ray crystallography (SCXC). SCXC also reveals that Au60S6(SCH2Ph)36 consists of a fcc-like Au20 kernel protected by a pair of giant Au20S3(SCH2Ph)18 staple motifs, which contain 6 tetrahedral-coordinate μ4-S atoms not previously reported in the Au–S interface. Importantly, the fourth crystallographic closest-packed pattern, termed 6H left-handed helical (6HLH) arrangement, which results in the distinct loss of solid photoluminescence of amorphous Au60S6(SCH2Ph)36, is found in the crystals of Au60S6(SCH2Ph)36. The solvent-polarity-dependent solution photoluminescence is also demonstrated. Overall, this work provides important insights about the structure, Au–S bonding and solid photoluminescence of gold nanoclusters.

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Section: Resultsmentioning

confidence: 99%

“…In particular, the structures of gold nanoclusters are of primary significance and have received the most extensive attention in the research community161718192021. However, structure achievements remain limited due to the difficulty of precise size control and structural resolution, especially for relatively large gold nanoclusters2223242526.…”

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The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

et al. 2017

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“…Therefore, the secondary block Au 13 (8e) has 91 variants of valence states (named as I 1 -I 91 ), as presented in 24 [28,37] clusters are shown in Figure 1, in which b in magenta, m in dark yellow, and t in yellow denote bottom flavor (1e), middle flavor (0.5e), and top flavor (0e), respectively. For example, with using the three Au "flavors" b, m, and t, I 79 can be rewritten as According to electron counting protocols of the GUM, each of the two surface gold atoms bonded with SR is assigned to transfer 0.5e valence electron to the staple motif.…”

Section: Resultsmentioning

confidence: 99%

Au13(8e): A secondary block for describing a special group of liganded gold clusters containing icosahedral Au13 motifs

Zeng

Gao

2017

Chemical Physics Letters

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A grand unified model (GUM) has been proposed recently to understand structure anatomy and evolution of liganded gold clusters. In this work, besidesthe two types of elementary blocks (triangular Au 3 (2e) and tetrahedral Au 4 (2e)), we introduce a secondary block, namely, the icosahedral Au 13 with 8e valence electrons, noted as Au 13 (8e). Using this secondary block, structural anatomy and evolution of a special group of liganded gold nanoclusters containing icosahedral Au 13 motifs can be conveniently analyzed. In addition, a new ligand-protected cluster Au 49 (PR 3 ) 10 (SR) 15 Cl 2 is predicted to exhibit high chemical and thermal stability, suggesting likelihood of its synthesis in the laboratory.

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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.…”

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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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Structural isomerism in gold nanoparticles revealed by X-ray crystallography

Cited by 271 publications

References 50 publications

The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

Au13(8e): A secondary block for describing a special group of liganded gold clusters containing icosahedral Au13 motifs

A grand unified model for liganded gold clusters

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