Photodriven electron transfer in triad molecules

A two-step charge recombination reaction

Devens Gust, Thomas Moore, Lewis R. Makings, Paul A. Liddell, Gregory A. Nemeth, Ana Moore

Research output: Contribution to journalArticle

71 Citations (Scopus)

Abstract

Excitation of carotenoid-porphyrin-quinone (C-P-Q) triad molecules initiates a two-step electron transfer to yield a final charge separated state of the form C•+-P-Q•-. This state has a very long lifetime in solution (10-7-10-6 s), and the nature of the ultimate charge recombination reaction has not previously been investigated. Nanosecond transient absorption spectroscopic studies have been performed on a series of such triad molecules wherein the nature of the linkages joining the porphyrin to the quinone and/or carotenoid moieties is varied systematically. The results reveal that charge recombination in C•+-P-Q•- does not occur in a single step but rather via an unusual two-step electron transfer involving an intermediate C-P•+-Q•- species. The temperature dependence is consistent with the formation of C-P•+-Q•- via a thermally activated process, and measurements over the range 221-296 K yield ΔH = 2.7 kcal/mol and ΔS = -20 cal/(deg·mol). The transient absorption measurements also reveal that the quantum yield of the C•+-P-Q•- state is a function of three electron transfer rate constants and that it can therefore be maximized by controlling the ratios of these rate constants to one another and to the rates of other pathways which depopulate the relevant excited states.

Original languageEnglish (US)
Pages (from-to)8028-8031
Number of pages4
JournalJournal of the American Chemical Society
Volume108
Issue number25
StatePublished - 1986

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Genetic Recombination
Porphyrins
Electrons
Carotenoids
Molecules
Rate constants
Quantum yield
Excited states
Joining
Temperature
benzoquinone

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Photodriven electron transfer in triad molecules : A two-step charge recombination reaction. / Gust, Devens; Moore, Thomas; Makings, Lewis R.; Liddell, Paul A.; Nemeth, Gregory A.; Moore, Ana.

In: Journal of the American Chemical Society, Vol. 108, No. 25, 1986, p. 8028-8031.

Research output: Contribution to journalArticle

Gust, Devens ; Moore, Thomas ; Makings, Lewis R. ; Liddell, Paul A. ; Nemeth, Gregory A. ; Moore, Ana. / Photodriven electron transfer in triad molecules : A two-step charge recombination reaction. In: Journal of the American Chemical Society. 1986 ; Vol. 108, No. 25. pp. 8028-8031.
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