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Journal Article

Absence of dielectric relaxation effects on intramolecular electron transfer in porphyrin-quinone cyclophanes

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Anders,  Christine
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Futscher,  Michael
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Staab,  Heinz A.
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Citation

Pöllinger, F., Heitele, H., Michel-Beyerle, M. E., Anders, C., Futscher, M., & Staab, H. A. (1992). Absence of dielectric relaxation effects on intramolecular electron transfer in porphyrin-quinone cyclophanes. Chemical Physics Letters, 198(6), 645-652. doi:10.1016/0009-2614(92)85043-A.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0019-AB1D-7
Abstract
We have measured photoinduced intramolecular electron transfer rates ket in two porphyrin-dichloroquinone cyclophanes varying the polarity, the temperature, and the dielectric relaxation time of the solvent. The reaction is most likely activationless or in the inverted region in all solvents. The adiabaticity parameter k = 4πV2eff/khλsτℓ for dynamic dielectric solvent control is estimated to cover the range 0.2 ⪕k ⪕ 400. Nevertheless the rate ket was found to be almost independent of the solvent properties (ket > 5 × 1011 s−1) casting doubt on current ideas of dielectric relaxation effects on electron transfer.