Emission of circularly-polarised radiation by optically-active compounds

Emeis, C.A.; Oosterhoff, L.J.

doi:10.1016/0009-2614(67)85007-3

Cited by 129 publications

(77 citation statements)

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“…The experimental spectra were recorded at room temperature in isooctane solution; however, it was determined that dilution and dissolution in methanol did not have a significant impact on the luminescence dissymmetry factor. [7] A modest red shift of 0.3 eV is necessary to match the positions of the main peaks of the calculated spectra with experiment, but the red shift of the emission and CPL spectra relative to the absorption and CD spectra is correctly reproduced by the computations. The calculated CD spectrum of hydrindanone has a similar envelope and correct spacing of the major vibrational peaks as seen in the experiment.…”

Section: Resultsmentioning

confidence: 91%

“…Data for the experimental spectra taken from Emeis and Oosterhoff. [7] Calculated spectra using the CAM-B3LYP/TZVP basis set have been shifted by À0.30 eV and broadened with s = 0.03 eV. The vertical line indicates the energy of the 0-0 transition.…”

Section: Resultsmentioning

confidence: 99%

“…The spectral bands in the region of 2-3 eV for camphorquinone and 3.5-6 eV for hydrindanone can be assigned to n!p*-type transitions associated with the carbonyl groups. Whereas the first electronic excited state of d-camphorquinone has a similar equilibrium geometry to the ground state, the excited-state equilibrium geometry of hydrindanone affords an out-of-plane bend of the carbonyl group (somewhat similar to that found in formaldehyde [7] ). The CD, CPL, UV/Vis absorption, and emission spectra of both of these molecules contain significant vibrational contributions that make them attractive targets for the modeling of their CPL spectra, their vibrational fine structure, and the overall band shapes, from first-principles theory.…”

Section: Introductionmentioning

confidence: 89%

“…The approach taken here is based on the method by Santoro et al for computations of FC factors needed to obtain the vibronic fine structure for absorption and emission spectra, with a focus on modeling CPL. Two molecules for which well-resolved CPL spectra have been reported are d-camphorquinone [17] and (S,S)-trans-b-hydrindanone [7] (Scheme 1). The spectral bands in the region of 2-3 eV for camphorquinone and 3.5-6 eV for hydrindanone can be assigned to n!p*-type transitions associated with the carbonyl groups.…”

Section: Introductionmentioning

confidence: 98%

“…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. [5][6][7] Large organometallic systems containing lanthanoids have been experimentally studied using CPL spectroscopy; however, the size of these systems is not presently conducive to ab initio calculations of vibrationally resolved spectra (even under the Franck-Condon approximation), particularly if the approach requires optimized excited-state geometries and calculations of vibrational frequencies and normal modes of the excited states. Small to medium sized organic molecules (particularly chiral ketones) can be theoretically studied starting from first principles.…”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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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Absolute Chiral Structures of Inorganic Compounds

Riehl

Kaizaki

2010

Physical Inorganic Chemistry

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Chiral inorganic compounds play increasingly important roles in current research efforts concerned with asymmetric catalysis, biochemistry, and supramolecular chemistry. Although our ability to determine precise chiral structures of inorganic compounds and relate these structures to chemical phenomena is a relatively recent achievement, this area of research has been a central and fundamental subject since the beginning of modern chemistry. The realization that substances other than those containing tetrahedral carbon atoms could occur as nonsuperimposable mirrorimage forms was first made by the "father of coordination chemistry" Alfred Werner at the end of the nineteenth century. 1 A critical consequence of his octahedral coordination theory was that certain isomers of six-coordinate metal complexes should exist as enantiomeric pairs. As early as 1897, Werner was speculating on whether or not he could verify the existence of mirror-image compounds from sixcoordinate octahedral geometry, and the preparation and resolution of a chiral molecular metal complex was finally achieved by his research colleagues Ernst Scholze and Victor L. King with the publication of the separation of the optical isomers (enantiomers) of cis-bromoamminebis(ethylenediamine)cobalt(III) salts in 1911. 2 Figure 5.1 illustrates the structure of the two possible mirror-image structures for this complex. The separated complexes were shown to possess equal and opposite optical rotations (OR) confirming their mirror-image relationship. Alfred Werner received the Nobel Prize in Chemistry for his development of the coordination theory 2 years after the publication of this milestone work in 1913.Following the experimental results of Werner and his colleagues, a number of theoretical attempts were made to correlate the sign and magnitude of the optical rotation to the exact chiral molecular structure of metal complexes. These approaches have been summarized by Richardson. 3 The term "absolute structure" is sometimes limited to a discussion of the structure of noncentrosymmetric crystals, and the term Physical Inorganic Chemistry: Principles, Methods, and Models Edited by Andreja Bakac

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