Effect of donor-acceptor orientation on ultrafast photoinduced electron transfer and dark charge recombination in porphyrin-quinone molecules

Yoshiteru Sakata, Hirohito Tsue, Michael P. O'Neil, Gary P. Wiederrecht, Michael R Wasielewski

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Abstract

A series of four zinc porphyrin-spacer-benzoquinone molecules were studied in which the spacer is either spiro[4.4] nonane or trans-decalin. The benzoquinone is attached to the porphyrin at two fixed distances each possessing two fixed orientations of the porphyrin relative to the quinone. The rate constants for photoinduced electron transfer from the lowest excited singlet state of the porphyrin to the quinone to form the Zn porphyrin+-quinone- ion pair and the subsequent dark charge recombination reaction were measured as a function of solvent polarity. The observed orientation dependent differences in rate constants for these two reactions can be attributed to orientation dependent changes in electronic coupling alone, because the Franck-Condon factors for electron transfer are similar for each molecule. The rate constant data suggest that the donor-acceptor orientation effects observed are due to variations in the sum of the direct, through-space interaction between the donor and acceptor and the indirect, through-solvent term. The rate constant data and AMI molecular orbital calculations support the idea that the indirect interaction of the donor with the acceptor through the covalent bonds of the spacer is approximately constant for the spacers employed in this study.

Original languageEnglish
Pages (from-to)6904-6909
Number of pages6
JournalJournal of the American Chemical Society
Volume116
Issue number15
Publication statusPublished - Jul 27 1994

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Porphyrins
Genetic Recombination
Electrons
Rate constants
Molecules
Transfer Factor
Orbital calculations
Covalent bonds
Molecular orbitals
Excited states
Zinc
benzoquinone
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Effect of donor-acceptor orientation on ultrafast photoinduced electron transfer and dark charge recombination in porphyrin-quinone molecules. / Sakata, Yoshiteru; Tsue, Hirohito; O'Neil, Michael P.; Wiederrecht, Gary P.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 116, No. 15, 27.07.1994, p. 6904-6909.

Research output: Contribution to journalArticle

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AU - Wiederrecht, Gary P.

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AB - A series of four zinc porphyrin-spacer-benzoquinone molecules were studied in which the spacer is either spiro[4.4] nonane or trans-decalin. The benzoquinone is attached to the porphyrin at two fixed distances each possessing two fixed orientations of the porphyrin relative to the quinone. The rate constants for photoinduced electron transfer from the lowest excited singlet state of the porphyrin to the quinone to form the Zn porphyrin+-quinone- ion pair and the subsequent dark charge recombination reaction were measured as a function of solvent polarity. The observed orientation dependent differences in rate constants for these two reactions can be attributed to orientation dependent changes in electronic coupling alone, because the Franck-Condon factors for electron transfer are similar for each molecule. The rate constant data suggest that the donor-acceptor orientation effects observed are due to variations in the sum of the direct, through-space interaction between the donor and acceptor and the indirect, through-solvent term. The rate constant data and AMI molecular orbital calculations support the idea that the indirect interaction of the donor with the acceptor through the covalent bonds of the spacer is approximately constant for the spacers employed in this study.

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