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Role of charge transfer and spin-orbit coupling in fluorescence quenching : a case study with oxonine and substituted benzenes

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1990

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Föll, Rudolf E.
Kramer, Horst E. A.

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Journal of Physical Chemistry. 1990, 94(6), pp. 2476-2487. ISSN 0022-3654. eISSN 1541-5740

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Fluorescence quenching of oxonine in methanol was investigated by means of a computerized dye laser flash spectrometer for the ∆G°et, dependence of the quenching rate constant (kq) and the efficiencies of induced dye triplet formation (ηT), reduced dye radical formation (ηR), and induced internal conversion. A total of 34 substituted benzenes including 20 monohalogenated benzenes, toluenes, and anisoles were used as quenchers spanning a range of -0.85 ≤ ∆G°et ≤ 1.4 eV for a possible photoelectron-transfer reaction with the dye singlet as electron acceptor. Induced internal conversion was the dominating channel in all cases. Free-radical formation was less than 2.0% throughout. Induced triplet formation was only detectable with heavy-atom-substituted quenchers and with ∆G°et ≥ -0.13 eV such that the free energy of the radical pair was not below the triplet energy of oxonine. In spite of a wide variation of kq the efficiency ηT was almost constant for a set of quenchers with the same halogen substituent.

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ISO 690FÖLL, Rudolf E., Horst E. A. KRAMER, Ulrich STEINER, 1990. Role of charge transfer and spin-orbit coupling in fluorescence quenching : a case study with oxonine and substituted benzenes. In: Journal of Physical Chemistry. 1990, 94(6), pp. 2476-2487. ISSN 0022-3654. eISSN 1541-5740
BibTex
@article{Foll1990charg-9940,
  year={1990},
  title={Role of charge transfer and spin-orbit coupling in fluorescence quenching : a case study with oxonine and substituted benzenes},
  number={6},
  volume={94},
  issn={0022-3654},
  journal={Journal of Physical Chemistry},
  pages={2476--2487},
  author={Föll, Rudolf E. and Kramer, Horst E. A. and Steiner, Ulrich}
}
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