The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

Goldsmith, Michael‐Rock; George, Christopher B.; Zuber, Gérard; Naaman, Ron; Wipf, Peter; Beratan, David N.

doi:10.1039/b511563a

Cited by 138 publications

(179 citation statements)

References 18 publications

(21 reference statements)

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“…[55,69] Goldsmith and coworkers demonstrated that optical activity could arise from an achiral metal core perturbed by a dissymmetric field originating from the chiral organic shell. [56] In the intermediate model, the grand core can be achiral but the relaxation of the surface atoms involved in the adsorption of the chiral ligand creates a chiral "footprint", like that observed for adsorption of tartaric acid on Ni surfaces (C). [57] This is favored for ligands that have at least two anchoring points on the surface.…”

Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 98%

“…Reproduced from ref. [56] with permission of the PCCP Owner Societies. C) Chiral footprint imparted by bitartrate on NiA C H T U N G T R E N N U N G (100) surface.…”

Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 99%

“…Models A and B have support from theoretical calculations. [55,56,69] Garzón et al have predicted that small metal particles such as Au 28 or Au 55 prefer low-symmetry chiral over highsymmetry nonchiral structures. [55,69] Goldsmith and coworkers demonstrated that optical activity could arise from an achiral metal core perturbed by a dissymmetric field originating from the chiral organic shell.…”

Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 99%

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Chiral Gold Nanoparticles

2009

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Monolayer-protected gold nanoparticles have many appealing physical and chemical properties such as quantum size effects, surface plasmon resonance, and catalytic activity. These hybrid organic-inorganic nanomaterials have promising potential applications as building blocks for nanotechnology, as catalysts, and as sensors. Recently, the chirality of these materials has attracted attention, and application to chiral technologies is an interesting perspective. This minireview deals with the preparation of chiral gold nanoparticles and their chiroptical properties. On the basis of the latter, together with predictions from quantum chemical calculations, we discuss different models that were put forward in the past to rationalize the observed optical activity in metal-based electronic transitions. We furthermore critically discuss these models in view of recent results on the structure determination of some gold clusters as well as ligand-exchange experiments examined by circular dichroism spectroscopy. It is also demonstrated that vibrational circular dichroism can be used to determine the structure of a chiral adsorbate and the way it interacts with the metal. Finally, possible applications of these new chiral materials are discussed.

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Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 98%

“…Reproduced from ref. [56] with permission of the PCCP Owner Societies. C) Chiral footprint imparted by bitartrate on NiA C H T U N G T R E N N U N G (100) surface.…”

Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 99%

Section: Possible Mechanism and Theoretical Studiesmentioning

confidence: 99%

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Chiral Gold Nanoparticles

2009

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“…11,[13][14][15][16][17][18][19] This shows that chirality can be bestowed to the metal. However, the question whether the metal core adopts an intrinsically chiral structure 20 or whether the chirality is only imposed on to the electronic structure of the metal core 21 remains still unanswered.…”

Section: Introductionmentioning

confidence: 99%

Chiral 1,1′‐binaphthyl‐2,2′‐dithiol‐stabilized gold clusters: Size separation and optical activity in the UV–vis

et al. 2007

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Gold particles covered with 1,1'-binaphthyl-2,2'-dithiol (BINAS) were prepared. Using size exclusion chromatography, it was possible for the first time to separate the sample into fractions with different sizes and colors. Transmission electron microscopy shows that the particles are very small, in the order of 1 nm or slightly above. The absorption spectra of the separated samples show rich structure. The particles show size-dependent optical activity in metal-based electronic transitions. The shape of both the absorption and circular dichroism spectra of one of the smallest fractions exhibits similarities with the spectra reported for Au 11 covered by 2,2'-bis(diphenylphosphino)-1,1'-biphenyl although the spectra are shifted to shorter wavelengths in the case of the dithiol. The anisotropy factors, Delta epsilon/epsilon of these particles are as large as 4 x 10(-3), which is larger than the values reported for gold particles stabilized by phosphines and water-soluble thiols. This indicates that BINAS is particularly well-suited to impart chirality on to gold particles.

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“…[60] Combined with plasmonic metal materials, multifarious chiral metamolecules have been designed. [30,61,62] Com paring to the natural chiral molecule, artificial metamolecules acted as versatile platforms to manipulate electric field at the nanoscale with negative index. [63] Because SPs are sensitive to the surrounding medium, and the material permittivity and morphology, plasmonic chiral metamolecules can display strong chiroptical response and high sensitivity to the CPL incidence.…”

Section: Plasmonic Chiral Metamoleculesmentioning

confidence: 99%

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

Luo

Chi

Jiang

et al. 2017

Advanced Optical Materials

161

122

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(circular birefringence) and absorption losses (circular dichroism) with the circu larly polarized light (CPL) illumination. [10] CB arises from the difference in the real part of refractive index, leading to a dif ferent velocity for LCP and RCP compo nents, and thus results in the polarization rotation of the linearly polarized incident light. CD corresponds to the difference in the imaginary part of refractive index, resulting in a distinct absorption loss for LCP and RCP excitations. Besides the con ventional CD and CB, asymmetric trans mission (circular conversion dichroism) is another fundamental chiroptical pheno menon, which exists in the nondiffracting array, referring to different LCPtoRCP and RCPtoLCP conversion efficiencies. [11] All of these chiroptical phenomena have been successfully applied in the spectros copy for identifying special arrangements of chiral matters in biology, chemistry and physics as efficient diagnostic tools. [12][13][14][15][16] However, the chirop tical response in natural chiral materials is relatively weak due to the small electromagnetic (EM) interaction volume, [17] hence limits its further applications.Recent progress in plasmonics paves the way for the enhancement of chiroptical response. [18][19][20] Surface plasmons (SPs), as the collective electrons oscillation at the dielectric and metal interface, [21][22][23] present the capacity of light confine ment and field enhancement, which significantly improve the strength of lightmatter interactions. [24][25][26][27][28] With the uptodate nanofabrication technology, the study field of chirality has been extended from traditional chiral molecules to 3D metallic nanostructures. [29][30][31][32] Chiroptical responses of metallic meta molecules have been widely investigated, [33][34][35] and applied in various fields, such as biosensing, [36] chiral catalysis, [37] polari zation tuning, [38] and chiral photo detection.[39] The 3D metallic structure exhibited giant optical activity response because of the strong interaction between electric and magnetic resonant modes. [40,41] Different from 3D chiral ensembles, planar chiral structures show none chiral effect, as they can always coincide with their mirror images. However, 2D chirality was successfully found in the quasitwodimensional (quasi2D) chiral structure. [42] Moreover, recent reports show that even achiral nanomaterials have the ability to generate strong CD under an oblique CPL illumination. [43] This kind of extrinsic chirality arises from sym metry breaking of the incident light and the quasi2D material, which is quite different from the intrinsic chirality of 3D chiral The plasmonic chiroptical effect has been used to manipulate chiral states of light, where the strong field enhancement and light localization in metallic nanostructures can amplify the chiroptical response. Moreover, in metamaterials, the chiroptical effect leads to circular dichroism (CD), circular birefringence (CB), and asymmetric transmission. Potential applications enabled by chiral plasmonics...

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The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates

Cited by 138 publications

References 18 publications

Chiral Gold Nanoparticles

Chiral Gold Nanoparticles

Chiral 1,1′‐binaphthyl‐2,2′‐dithiol‐stabilized gold clusters: Size separation and optical activity in the UV–vis

Plasmonic Chiral Nanostructures: Chiroptical Effects and Applications

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