Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads

Alisdair N. Macpherson, Paul A. Liddell, Su Lin, Lori Noss, Gilbert R. Seely, Janice M. DeGraziano, Ana L Moore, Thomas A Moore, John Devens Gust

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Abstract

Three dyad molecules, each consisting of a porphyrin (P) linked to a quinone (Q) through a rigid bicyclic bridge, have been prepared, and their photochemistry has been investigated using time-resolved fluorescence and absorption techniques. In all three molecules, photoinduced electron transfer from the porphyrin first excited singlet state to the quinone occurs with rate constants of ∼1012 s-1 in solvents ranging in dielectric constant from ∼2.0 to 25.6 and at temperatures from 77 to 295 K. The transfer rate is also relatively insensitive to thermodynamic driving force changes up to 0.4 eV. This behavior is phenomenologically similar to photosynthetic electron transfer. The rapid rate of photoinduced electron transfer and its lack of dependence on environmental factors suggests that transfer is governed by intramolecular vibrations. Charge recombination of P.+-Q.-, on the other hand, is substantially slower than charge separation and sensitive to both driving force and environmental conditions. Thus, by changing conditions, charge recombination rates can be varied over a wide range while photoinduced electron transfer rates are relatively unaffected. This suggests that rigid dyads of this general type may be useful building blocks for more complex molecular devices.

Original languageEnglish
Pages (from-to)7202-7212
Number of pages11
JournalJournal of the American Chemical Society
Volume117
Issue number27
Publication statusPublished - Jul 12 1995

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Porphyrins
Electrons
Genetic Recombination
Photochemistry
Transfer Factor
Molecules
Photochemical reactions
Vibration
Thermodynamics
Excited states
Rate constants
Permittivity
Fluorescence
Equipment and Supplies
Temperature
benzoquinone

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Macpherson, A. N., Liddell, P. A., Lin, S., Noss, L., Seely, G. R., DeGraziano, J. M., ... Gust, J. D. (1995). Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads. Journal of the American Chemical Society, 117(27), 7202-7212.

Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads. / Macpherson, Alisdair N.; Liddell, Paul A.; Lin, Su; Noss, Lori; Seely, Gilbert R.; DeGraziano, Janice M.; Moore, Ana L; Moore, Thomas A; Gust, John Devens.

In: Journal of the American Chemical Society, Vol. 117, No. 27, 12.07.1995, p. 7202-7212.

Research output: Contribution to journalArticle

Macpherson, AN, Liddell, PA, Lin, S, Noss, L, Seely, GR, DeGraziano, JM, Moore, AL, Moore, TA & Gust, JD 1995, 'Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads', Journal of the American Chemical Society, vol. 117, no. 27, pp. 7202-7212.
Macpherson AN, Liddell PA, Lin S, Noss L, Seely GR, DeGraziano JM et al. Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads. Journal of the American Chemical Society. 1995 Jul 12;117(27):7202-7212.
Macpherson, Alisdair N. ; Liddell, Paul A. ; Lin, Su ; Noss, Lori ; Seely, Gilbert R. ; DeGraziano, Janice M. ; Moore, Ana L ; Moore, Thomas A ; Gust, John Devens. / Ultrafast photoinduced electron transfer in rigid porphyrin-quinone dyads. In: Journal of the American Chemical Society. 1995 ; Vol. 117, No. 27. pp. 7202-7212.
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