Correlating the Structure and Optical Absorption Properties of Au<sub>76</sub>(SR)<sub>44</sub> Cluster

Ma, Zhongyun; Wang, Pu; Zhou, Guohui; Tang, Jian; Li, Hengfeng; Pei, Yong

doi:10.1021/acs.jpcc.6b04212

Cited by 32 publications

(33 citation statements)

References 87 publications

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“…The three most stable sizes identified in this study, i.e., [Au 25 (SR) 18 ] − (icosahedral Au 13 core) 10 , 56 , [Au 38 (SR) 24 ] 0 (fused bi-icosahedral Au 23 core) 55 , and [Au 44 (SR) 26 ] 2− (bottom-capped bi-icosahedral Au 29 core) 15 , constitute a new magic size series based on the icosahedral Au 13 unit, which are distinctly different from the face-centered cubic (FCC)-based magic size series, Au 8 N +4 (SR) 4 N +8 (e.g., Au 28 (SR) 20 , Au 36 (SR) 24 , Au 44 (SR) 28 , Au 52 (SR) 32 , and Au 76 (SR) 44 ) recently revealed by both experimental and theoretical means 57 , 58 . The cluster cores in the latter are constructed by successively packing Au 8 layer in (001) direction, which is vastly different from fusion of the icosahedral Au 13 units in the former.…”

Section: Resultsmentioning

confidence: 86%

Understanding seed-mediated growth of gold nanoclusters at molecular level

et al. 2017

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The continuous development of total synthesis chemistry has allowed many organic and biomolecules to be produced with known synthetic history–that is, a complete set of step reactions in their synthetic routes. Here, we extend such molecular-level precise reaction routes to nanochemistry, particularly to a seed-mediated synthesis of inorganic nanoparticles. By systematically investigating the time−dependent abundance of 35 intermediate species in total, we map out relevant step reactions in a model size growth reaction from molecularly pure Au25 to Au44 nanoparticles. The size growth of Au nanoparticles involves two different size−evolution processes (monotonic LaMer growth and volcano-shaped aggregative growth), which are driven by a sequential 2-electron boosting of the valence electron count of Au nanoparticles. Such fundamental findings not only provide guiding principles to produce other sizes of Au nanoparticles (e.g., Au38), but also represent molecular-level insights on long-standing puzzles in nanochemistry, including LaMer growth, aggregative growth, and digestive ripening.

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Section: Resultsmentioning

confidence: 86%

Understanding seed-mediated growth of gold nanoclusters at molecular level

et al. 2017

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“…But increasing of anisotropy during the growth of nanoclusters would make them more challenge to be synthesized. Theoretical calculations have provided some insights on the further evolution of the properties of this periodic series [78,79]. It is worth noting the formula of Au 20 (TBBT) 16 also falls into the magic series (i.e.…”

Section: Periodicity: a Series Of Gold Quantum Boxesmentioning

confidence: 95%

Precision at the nanoscale: on the structure and property evolution of gold nanoclusters

Zeng

2018

Pure and Applied Chemistry

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Chemists are often regarded as “architects”, who are capable of building up complex molecular structures in the ultrasmall-dimensional world. However, compared with organic chemistry, nanochemistry – which deals with nanoparticles in the size range from 1 to 100 nm – is less precise in terms of synthesis, composition, and structure. Such an imprecise nature of nanochemistry has impeded an in-depth understanding as well as rational control of structures and properties of nanomaterials. Motivated by this, thiolate-protected gold nanoclusters (denoted as Aun(SR)m) have recently emerged as a paradigm of atomically precise nanomaterials, in which all the nanoparticles are identical to each other with the same number of core atoms (n) and surface ligands (m) as well as the atomic arrangement. In this review, we provide a demonstration of how the precise nature of Aun(SR)m nanoclusters allows one to understand, decipher and discover some important, enigmatic and intriguing issues and phenomena in nanoscience, including (i) a precise nanoscale transformation reaction induced by surface ligand exchange, (ii) the total structures of crystalline metal phases and the self-assembled surface monolayers, (iii) the periodicities and quantum confinement in nanoclusters and (iv) the emergence of hierarchical complexity in the entire nanoparticle system. We expect that such an in-depth understanding will eventually lead to the rational design and precise engineering of complex architectures at the nanoscale.

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“…The other examples are Au 14+6 N ((8 + 4 N )e) with N = 1–3, 6 [ 105–118 ] in which two vertex‐sharing oligomers of Au 4 (2e) are assembled into a double helix structure. In Table 5, existence of two oligomers colored in blue and purple is recognized by highlighting the AuAu bonds shorter than those in bulk Au (2.88 Å).…”

Section: Effect Of Shape: Nonspherical Superatomsmentioning

confidence: 99%

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

Omoda

Takano

Tsukuda

2020

Small

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Atomically precise gold/silver clusters protected by organic ligands L, [(Au/Ag)xLy]z, have gained increasing interest as building units of functional materials because of their novel photophysical and physicochemical properties. The properties of [(Au/Ag)xLy]z are intimately associated with the quantized electronic structures of the metallic cores, which can be viewed as superatoms from the analogy of naked Au/Ag clusters. Thus, establishment of the correlation between the geometric and electronic structures of the superatomic cores is crucial for rational design and improvement of the properties of [(Au/Ag)xLy]z. This review article aims to provide a qualitative understanding on how the electronic structures of [(Au/Ag)xLy]z are affected by geometric structures of the superatomic cores with a focus on three factors: size, shape, and composition, on the basis of single‐crystal X‐ray diffraction data. The knowledge accumulated here will constitute a basis for the development of ligand‐protected Au/Ag clusters as new artificial elements on a nanometer scale.

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Correlating the Structure and Optical Absorption Properties of Au₇₆(SR)₄₄ Cluster

Cited by 32 publications

References 87 publications

Understanding seed-mediated growth of gold nanoclusters at molecular level

Understanding seed-mediated growth of gold nanoclusters at molecular level

Precision at the nanoscale: on the structure and property evolution of gold nanoclusters

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

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Correlating the Structure and Optical Absorption Properties of Au76(SR)44 Cluster

Cited by 32 publications

References 87 publications

Understanding seed-mediated growth of gold nanoclusters at molecular level

Understanding seed-mediated growth of gold nanoclusters at molecular level

Precision at the nanoscale: on the structure and property evolution of gold nanoclusters

Toward Controlling the Electronic Structures of Chemically Modified Superatoms of Gold and Silver

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Correlating the Structure and Optical Absorption Properties of Au₇₆(SR)₄₄ Cluster