Racemization of a Chiral Nanoparticle Evidences the Flexibility of the Gold–Thiolate Interface

Knoppe, Stefan; Dolamic, Igor; Bürgi, Thomas

doi:10.1021/ja3053865

Cited by 111 publications

(167 citation statements)

References 48 publications

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“…Coinagem etal nanostructures have received considerable interest owing to their unique physicala nd chemical behavior, [1][2][3][4][5][6][7][8][9][10] delivering promising buildingb locks for functional nanomaterials. Particularly,t he knowledge of stable gold clusters has been well developed leading to the understanding of both structural and electronic properties, [11][12][13][14][15][16][17][18] with promising applicationsi nb iomedicine, catalysis, and sensing, among others.…”

Section: Introductionmentioning

confidence: 99%

Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

Gam

Páez‐Hernández

Arratia‐Pérez

et al. 2017

Chemistry A European J

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Coinage-metal atomically precise nanoclusters are made of a well-defined metallic core embedded in a ligand-protecting outer shell. Whereas gold derivatives are particularly well documented, examples of silver nanoclusters are somewhat limited and copper species remain particularly scare. Our DFT relativistic calculations on superatomic metallic cores indicate that copper species are almost as stable as gold clusters and more stable than their silver counterparts. Thus, for silver superatomic cores, the role of the stabilizing ligands is more crucial in the stabilization of the overall structure, in comparison to copper and gold. Hence, the chemistry of the earlier counterparts of gold, especially copper, should grow quickly with at least characterizations of species related to that found in the heavier elements in the triad, which requires tackling synthetic challenges. Time-dependent (TD)-DFT calculations show that with an increase of the cluster core nuclearity, the absorption bands are redshifted, allowing us to differentiate between the clusters types. Moreover, the optical properties of the silver cores are fairly different from that of their Cu and Au relatives.

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Section: Introductionmentioning

confidence: 99%

Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

Gam

Páez‐Hernández

Arratia‐Pérez

et al. 2017

Chemistry A European J

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“…The energy barrier to interconversion of the enantiomers is low, so the cluster loses optical activity at at 40 8C. 202 This makes the cluster of limited use in asymmetric catalysis and as component of chiral sensors at temperatures above 40 8C. The problem can be solved by introducing one or two 1,1 Hbinaphthyl-2,2 H -dithiol substituents into the cluster.…”

Section: Methods For Determination Of the Structure And Propertiementioning

confidence: 99%

Ligand-protected gold clusters: the structure, synthesis and applications

Пичугина¹,

Кузьменко²,

Shestakov³

2015

Russ. Chem. Rev.

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“…[101] Later calculations found that ac hiral arrangement of the two propellers could furtherl ower the energy, [102] which is ar esult of the minimization of steric stress between the staple motifs. [105] Qian et al [106] also performed an NMR spectroscopy analysis on the racemic Au 38 (SR) 24 (R = CH 2 CH 2 Ph) nanoclusters and observed an interesting diastereotopicity effect in the two geminal protons in each CH 2 of the SCH 2 CH 2 Ph ligands on thec hiral Au 38 (SR) 24 nanocluster (Scheme 1). The separated enantiomers showed normal opticala bsorption peaks at l = 490, 520, 560, 620, and 750 nm (Figure 5a), which are the same as the peaks of the racemic mixture.…”

Section: With An Biicosahedral Kernelmentioning

confidence: 99%

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality

Zeng

Jin

2017

Chemistry An Asian Journal

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Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au (SR) ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au (SR) structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au (SR) and Au (SR) nanoclusters. Overall, the origins of chirality discovered in Au (SR) nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles.

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Racemization of a Chiral Nanoparticle Evidences the Flexibility of the Gold–Thiolate Interface

Cited by 111 publications

References 48 publications

Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

Coinage Metal Superatomic Cores: Insights into Their Intrinsic Stability and Optical Properties from Relativistic DFT Calculations

Ligand-protected gold clusters: the structure, synthesis and applications

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality

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