The Dispersion and other Chiral Discriminations

Mason, S. F.

doi:10.1007/978-94-015-7644-4_13

Cited by 80 publications

(124 citation statements)

References 24 publications

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“…Through static coupling, [28] the 4f orbitals mix with other orbitals, usually with 4f NÀ1 5d or 4f NÀ1 ng configurations, to obtain odd-parity states, and this contributionismade possible by the presence of adissymmetric ligand field. Dynamic coupling [29] considers that the leadinge lectric quadrupole moment of the lanthanide transition induces, andc ouples to, as econdary transiente lectric transition dipole momenti ne ach ligand group:t his mechanism is strictly ligand polarization dependent.T he magnetic dipole moment fort he transition a!b can be calculated at 0th order (no need to invoke the perturbation Hamiltonian) as [Eq. (13)]: …”

Section: Theoretical Backgroundmentioning

confidence: 99%

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes

Berardozzi

Bari

2015

ChemPhysChem

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We used a very simplified electrostatic model based on charge and polarizability of atoms and groups on an organic ligand around a lanthanide ion to predict the near-infrared electronic circular dichroism (NIR ECD) spectra of Yb (a monoelectronic ion). We tuned our method by using two widely different complexes. The first was the heterobimetallic species CsYb(hfbc) [hfbc=(-)-3-heptafluorobutyrylcamphorate], in which the ligand is a diketonate and, as such, is endowed with a chromophore with strong UV absorption (π-π ). Its oxygen atoms define a square antiprism, which provides a symmetric coordination polyhedron. The second system was Yb DOTMA [DOTMA=(1R,4R,7R,10R)-α,α',α'',α'''-tetramethyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid], a chiral Yb analogue of Gd DOTA (DOTA=1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid), in which the ligand lacks relevant electronic transitions and provides a dissymmetric cage. The relative weights of dynamic (ligand polarization) and static contributions to Yb NIR ECD were evaluated, and the spectra appear to have been well predicted by theory through the introduction of a heuristic weight factor. To validate the approach and to confirm the value of the weight factor, we applied it to two other compounds, namely, Na Yb(BINOLate) and Yb(BINOLAM) [BINOLate=2,2'-dihydroxy-1,1'-binaphthyl; BINOLAM=3,3'-bis(diethylaminomethyl)-1-1'-bi-2-naphthol].

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Section: Theoretical Backgroundmentioning

confidence: 99%

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes

Berardozzi

Bari

2015

ChemPhysChem

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“…Much later the empirical evidence of the role of the forces of nature on the chiral compounds was obtained. The early idea of Pasteur was supported by modern experimental capabilities [133,134]. Two essential facts were observed: the effect of magnetic field on the molecular chirality [135] and increased enzyme stereo specificity in the course of an enzyme/protein evolution [136,137].…”

Section: Chirality Transfermentioning

confidence: 99%

The Chain of Chirality Transfer as Determinant of Brain Functional Laterality. Breaking the Chirality Silence: Search for New Generation of Biomarkers; Relevance to Neurodegenerative Diseases, Cognitive Psychology, and Nutrition Science

Dyakin¹,

Lucas²,

Dyakina‐Fagnano³

et al. 2017

NNR

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“…5, since the transition frequency does not change during the jump J(ϕ) = J(−ϕ). However, the jump rate is clearly seen in the decay of the peak volume with delay time t 2 . Equation (30) should be combined with Eqs.…”

Section: A Signatures Of Chirality Exchange In the 2d Spectrum Of Thmentioning

confidence: 99%

“…[2][3][4][5] The simplest and most common is a linear spectroscopic techniquecircular dichroism (CD): the difference between the absorption of left-and right-handed circularly polarized light. 6,7 Chirality of peptides is commonly investigated by vibrational circular dichroism in the infrared, or by Raman optical activity.…”

Section: Introductionmentioning

confidence: 99%

Novel coherent two-dimensional optical spectroscopy probes of chirality exchange and fluctuations in molecules

Šanda

Mukamel

2011

The Journal of Chemical Physics

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We demonstrate how stochastic transitions between molecular configurations with opposite senses of chirality may be probed by 2D optical signals with specific pulse polarization configurations. The third-order optical response of molecular dimers (such as biphenyls) with dynamical axial chirality is calculated to order of k 2 in the wavevector of light. Spectroscopic signatures of equilibrium chirality fluctuations are predicted for three dynamical models (Ornstein-Uhlenbeck, two-state jump, and diffusion in double well) of the dihedral angle that controls the chirality.

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The Dispersion and other Chiral Discriminations

Cited by 80 publications

References 24 publications

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes

The Chain of Chirality Transfer as Determinant of Brain Functional Laterality. Breaking the Chirality Silence: Search for New Generation of Biomarkers; Relevance to Neurodegenerative Diseases, Cognitive Psychology, and Nutrition Science

Novel coherent two-dimensional optical spectroscopy probes of chirality exchange and fluctuations in molecules

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The Dispersion and other Chiral Discriminations

Cited by 80 publications

References 24 publications

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb3+ Complexes

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb3+ Complexes

The Chain of Chirality Transfer as Determinant of Brain Functional Laterality. Breaking the Chirality Silence: Search for New Generation of Biomarkers; Relevance to Neurodegenerative Diseases, Cognitive Psychology, and Nutrition Science

Novel coherent two-dimensional optical spectroscopy probes of chirality exchange and fluctuations in molecules

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Product

Resources

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Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes

Optical Activity in the Near‐IR Region: The λ=980 nm Multiplet of Chiral Yb³⁺ Complexes