Correspondence: Reply to ‘On the bonding in ligand-protected gold clusters’

Xu, Wen; Zeng, Xiao Cheng; Gao, Yi

doi:10.1038/s41467-017-01294-w

Cited by 7 publications

(12 citation statements)

References 13 publications

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“…Thus, the ligand-protected [Au 6 (1,3-Bis(diphenylphosphino)propane) 4 ] 2+ and [Au 6 (PR 3 ) 6 ] 2+ can be well explained by the GUM. Note that the orbital analysis on the simple gold nanoclusters is quite similar as Mg dimer, in which 3 s orbitals (HOMO) of two Mg atoms can form the bonding (HOMO–1) and antibonding (HOMO) orbitals of Mg 2 (Figure c) …”

Section: Gummentioning

confidence: 99%

“…HOMO (d) and HOMO-1 (e) of [Au 6 (1,3-bis(diphenylphosphino)propane) 4 ] 2+ , HOMO (f) and HOMO-18 (g) of [Au 6 (PR 3 ) 6 ] 2+ . Adapted with permission from ref . Copyright 2017 Nature Publishing group.…”

Section: Gummentioning

confidence: 99%

“…Besides these successful crystallizations, a series of synthesized Au nanoclusters still await for structural determination. − In addition, some thiolate-protected Au nanoclusters have been theoretically predicted, whose computed UV–vis absorption spectra can well reproduce the experimental measurements. − The “big-data” of experimentally determined and theoretically predicted ligand-protected gold nanoclusters not only are useful to draw structure–property correlations, but also benefit the development of theoretical models to explain nanoclusters’ structures and stabilities. In Table , several established theoretical models, including the polyhedral skeletal electron pair theory (PSEPT), , spherical jellium model, − ellipsoidal shell model, “divide and protect” rule, superatom complex (SAC) model, super valence bond (SVB) model, superatom network (SAN) model, Borromean ring model, united cluster approach, and grand unified model (GUM), − are briefly summarized to show the high interest in developing theoretical models since the 1970s. Note that different models have different scopes of application and all have made successful predictions of certain crystallized structures, i.e., Au 25 (SR) 18 – and Au 38 (SR) 24 . , These theoretical models represent a significant advancement in describing special stabilities of ligand-protected gold nanoclusters.…”

Section: Introductionmentioning

confidence: 99%

“…So exceptional cases to these models still abound. The recently developed GUM by us is an attempt to provide a generic description of the ligand-protected gold nanoclusters, in terms of packing the elementary blocks into an Au core, followed by adding the outmost ligand shell. − In this Account, the GUM is overviewed as a unique and generic theoretical model. Moreover, three notable applications of GUM, i.e., the structural evolution, structural isomerism, and rational design of ligand-protected gold nanocluster, are presented.…”

Section: Introductionmentioning

confidence: 99%

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Application of Electronic Counting Rules for Ligand-Protected Gold Nanoclusters

2018

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Conspectus Understanding special stability of numerous ligand-protected gold nanoclusters has always been an active area of research. In the past few decades, several theoretical models, including the polyhedral skeletal electron pair theory (PSEPT), superatom complex (SAC), and superatom network (SAN), among others, have been developed for better understanding the stabilities and structures of selected ligand-protected gold nanoclusters. This Account overviews the recently proposed grand unified model (GUM) to offer some new insights into the structures and growth mechanism of nearly all crystallized and predicted ligand-protected gold nanoclusters. The main conceptual advancement of the GUM is identification of the duet and octet rules on the basis of the “big data” of 70+ reported ligand-protected gold nanoclusters. According to the two empirical rules, the cores of the gold nanoclusters can be regarded as being composed of two kinds of elementary blocks (namely, triangle Au3 and tetrahedron Au4), each having 2e closed-shell valence electrons (referred as Au3(2e) and Au4(2e)), as well as the secondary block (icosahedron Au13) with 8e closed-shell valence electrons (referred as Au13(8e)). The two elementary blocks (Au3(2e) and Au4(2e)) and the secondary block (Au13(8e)), from electron counting point of view, can be regarded as an analogy of the highly stable noble-gas atoms of He and Ne, respectively. In each elementary block, the Au atoms exhibit three different valence-electron states (i.e., 1e, 0.5e, and 0e), depending on the type of ligands bonded with these Au atoms. Such three valence-electron states are coined as three “flavors” of gold (namely, bottom, middle, and top “flavor”), a term borrowed from the quark model in the particle physics. Upon application of the duet and octet rules with accounting the three valence states of gold atoms, the Au3(2e), Au4(2e), and Au13(8e) blocks can exhibit 10 (denoted as Δ1–Δ10), 15 (denoted as T1–T15), and 91 (denoted as I1–I91) variants of valence states, respectively. When packing these blocks (with distinct electronic states) together, it forms the gold core of ligand-protected gold nanocluster. As such, the special stabilities of the ligand-protected gold nanoclusters are explained based on the local stability of each block. With GUM, rich and complex structures of ligand-protected gold nanoclusters have been analyzed through structure anatomy. Moreover, the growth of these clusters can be simply viewed as sequential addition of the blocks, rather than as addition of the gold atoms. Another useful application of the GUM is to analyze the structural isomerism. The three types of isomerism for the gold nanoclusters, i.e., core, staple, and complex isomerism, can be considered as an analogy of chain, point, and functional isomerism (known in organic chemistry), respectively. GUM can be applied to predict new clusters, thereby guiding experimental synthesis. Indeed, a number of ligand-protected gold nanoclusters with high stabilities were rationally designed based on...

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Section: Gummentioning

confidence: 99%

Section: Gummentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Application of Electronic Counting Rules for Ligand-Protected Gold Nanoclusters

2018

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“…There exist attempts devoted to account or rationalize the structure of TGCs. A more recent approach is the grand unified model or GUM that describes the anatomy and evolution of TGCs in terms of elementary blocks such as charged Au 3 , Au 4 , and Au 13 units. Therefore, the GUM approach is able to explain their inner cores by the aggregation of elementary building blocks; for example, the electronic levels of Au 6 2+ can be seen as a linear combination of electronic levels of two elementary Au 3 + blocks…”

Section: Introductionmentioning

confidence: 99%

New Polyhedra Approach To Explain the Structure and Evolution on Size of Thiolated Gold Clusters

Tlahuice‐Flores

2019

J. Phys. Chem. C

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Thiolated gold clusters (TGCs) have received a lot of attention in the nanoscience field in the last decade because of their potential applications that include catalysis, image diagnosis, photovoltaics, nanomedicine, and so forth. Their study has been fueled by the development of new synthesis, separation, and analysis methods in the experimental side and by new algorithms that are able to propose more reliable initial structures during theoretical predictions. Till date, there are more than 70 calculated/synthesized structures, displaying a variety in both their shapes and their constituting inner cores. When hundreds of atoms constitute TGCs, a description of their structures is not easy and they require a conceptual simplification. A simplified description of 36 reported structures of TGCs in terms of the assembly of elementary building blocks (tetrahedral or octahedral units) is proposed in this paper. It is expected that the obtained trends can be exploited during the prediction of new structures.

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Coinage metal clusters: From superatom chemistry to genetic materials

Yin

Luo

2021

Coordination Chemistry Reviews

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Correspondence: Reply to ‘On the bonding in ligand-protected gold clusters’

Cited by 7 publications

References 13 publications

Application of Electronic Counting Rules for Ligand-Protected Gold Nanoclusters

Application of Electronic Counting Rules for Ligand-Protected Gold Nanoclusters

New Polyhedra Approach To Explain the Structure and Evolution on Size of Thiolated Gold Clusters

Coinage metal clusters: From superatom chemistry to genetic materials

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