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Thermal cis-trans isomerization of solvatochromic merocyanines : linear correlations between solvent polarity and adiabatic and diabatic transition energies

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Datum

1988

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Abdel-Halim, Shakir T.
Abdel-Kader, Mahmoud H.

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http://nbn-resolving.de/urn:nbn:de:bsz:352-opus-46520
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https://doi.org/10.1021/j100326a017
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Attribution-NonCommercial-NoDerivs 2.0 Generic

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Published

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Journal of Physical Chemistry. 1988, 92(15), pp. 4324-4328. ISSN 0022-3654. eISSN 1541-5740. Available under: doi: 10.1021/j100326a017

Zusammenfassung

The correlation between solvatochromy and the solvent-polarity-dependent rate constant k ct of thermal cis-trans isomerization (solvatokinetic behavior) has been investigated for a stilbazolium-type merocyanine and an amphiphilic analogue in a polarity series of eight neat solvents (protic and aprotic). At room temperature k ct varies over 7 orders of magnitude, decreasing with increasing solvent polarity. It has been demonstrated that the first transition energy ∆E max and the free activation enthalpy ∆G* ct of thermal cis-trans isomerization are linearly correlated with each other and with Dimroth s solvent polarity parameter E T. These observations and the solvent-polarity-dependent increase of absorption band width are explained in terms of a model emphasizing the strong coupling between molecular conformation, electronic charge distribution, and solvent polarization.

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540 Chemie

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ISO 690ABDEL-HALIM, Shakir T., Mahmoud H. ABDEL-KADER, Ulrich STEINER, 1988. Thermal cis-trans isomerization of solvatochromic merocyanines : linear correlations between solvent polarity and adiabatic and diabatic transition energies. In: Journal of Physical Chemistry. 1988, 92(15), pp. 4324-4328. ISSN 0022-3654. eISSN 1541-5740. Available under: doi: 10.1021/j100326a017
BibTex
@article{AbdelHalim1988Therm-9997,
  year={1988},
  doi={10.1021/j100326a017},
  title={Thermal cis-trans isomerization of solvatochromic merocyanines : linear correlations between solvent polarity and adiabatic and diabatic transition energies},
  number={15},
  volume={92},
  issn={0022-3654},
  journal={Journal of Physical Chemistry},
  pages={4324--4328},
  author={Abdel-Halim, Shakir T. and Abdel-Kader, Mahmoud H. and Steiner, Ulrich}
}
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