Computing chiroptical properties with first‐principles theoretical methods: Background and illustrative examples

Autschbach, Jochen

doi:10.1002/chir.20789

Cited by 321 publications

(333 citation statements)

References 218 publications

(374 reference statements)

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“…[1][2][3][4] Whereas the strength of CD spectroscopy lies mainly in the ability to determine the stereochemistry of the ground electronic state, its emission analogue, circularly polarized luminescence [5] (CPL, sometimes called "circularly polarized emission") spectroscopy, has the ability to probe additional features of the excited electronic state from which the emission occurs. Combined information from CD and CPL experiments can allow for a more detailed analysis of the transitions; in particular, information can be obtained about stereochemical, conformational, and configurational changes undergone by the molecule upon excitation that are not available from CD experiments alone.…”

Section: Introductionmentioning

confidence: 99%

Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Pritchard

Autschbach

2010

ChemPhysChem

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Circularly polarized luminescence (CPL), the differential emission of left- and right-handed circularly polarized light from a molecule, is modeled by using time-dependent density functional theory. Calculations of the CPL spectra for the first electronic excited states of d-camphorquinone and (S,S)-trans-beta-hydrindanone under the Franck-Condon approximation and using various functionals are presented, as well as calculations of absorption, emission, and circular dichroism spectra. The functionals B3LYP, BHLYP, and CAM-B3LYP are employed, along with the TZVP and aug-cc-pVDZ Gaussian-type basis sets. For the lowest-energy transitions, all functionals and basis sets perform comparably, with the long-range-corrected CAM-B3LYP better reproducing the excitation energy of camphorquinone but leading to a blue shift with respect to experiment for hydrindanone. The vibrationally resolved spectra of camphorquinone are very well reproduced in terms of peak location, widths, shapes, and intensities. The spectra of hydrindanone are well reproduced in terms of overall envelope shape and width, as well as the lack of prominent vibrational structure in the emission and CPL spectra. Overall the simulated spectra compare well with experiment, and reproduce the band shapes, emission red shifts, and presence or absence of visible vibrational fine structure.

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Section: Introductionmentioning

confidence: 99%

Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Pritchard

Autschbach

2010

ChemPhysChem

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“…[4,5] However,w hile NMR spectroscopy in itself is not sensitive to chirality but, for instance,t ot he formation of diastereomers,electronic transitions observed in ECD usually feature quite broad absorbance bands.T his may complicate the interpretation of the spectra, as,f or instance,b ands of cations and anions featuring similar chromophors can overlap,s olvent absorbance might cover important transitions, and the prediction of ECD band intensities and signs can be challenging. [6] Clearly,additional methods and techniques are required to investigate chiral ion pairing systems.…”

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confidence: 99%

Stereochemical Communication within a Chiral Ion Pair Catalyst

et al. 2015

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Ionic interactions are increasingly appreciated as a key, asymmetry-inducing factor in enantioselective catalytic transformations, including those involving Brønsted acid or base catalysis, phase-transfer catalysis, and related processes. However, a detailed understanding of these interactions is often lacking. Herein, we show how an enantiopure anion enforces a chiral conformation onto a catalytically relevant achiral cation. Specifically, we use vibrational circular dichroism (VCD) spectroscopy to monitor the transmission of stereochemical information from a chiral phosphate anion to a flexible manganese(III)-salen cation. We show that VCD can be used to study solvent effects and that the obtained chiroptical data directly and quantitatively correlate with the experimentally observed enantioselectivity in an asymmetric olefin epoxidation reaction.

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“…To assign the absolute configurations, electronic CD spectra were measured and calculated with the TDDFT method. 18 The experimental UV absorption and CD spectra of (+)-1 and (-)-2 in methanol are almost coincident (Fig. 1).…”

Section: Computational Sectionmentioning

confidence: 69%

Isolation, Stereochemical Study, and Cytotoxic Activity of Isobenzofuran Derivatives From a Marine Streptomyces sp.

Zhang

Shen

et al. 2014

Chirality

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A new 1,3-dihydroisobenzofuran derivative (), together with its epimer (), was isolated from marine Streptomyces sp. W007. The structure of the two compounds was established by extensive spectroscopic analysis and comparison with reported data. The absolute configurations of and were determined by a combination of experimental and computational means, including J-coupling analysis and nuclear Overhauser effect spectroscopy (NOESY) spectra, nuclear magnetic resonance (NMR) calculations, electronic circular dichroism (ECD), and optical rotation (OR) calculations. Compound had no cytotoxicity against human lung adenocarcinoma cell line A549, while compound exhibited weak activity, suggesting that the biological activity depends on the configuration of a single chirality center.

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Computing chiroptical properties with first‐principles theoretical methods: Background and illustrative examples

Cited by 321 publications

References 218 publications

Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Calculation of the Vibrationally Resolved, Circularly Polarized Luminescence of d‐Camphorquinone and (S,S)‐trans‐β‐Hydrindanone

Stereochemical Communication within a Chiral Ion Pair Catalyst

Isolation, Stereochemical Study, and Cytotoxic Activity of Isobenzofuran Derivatives From a Marine Streptomyces sp.

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