Photoinduced electron transfer in a porphyrin dyad

Devens Gust, Thomas Moore, Ana Moore, Lana Leggett, Su Lin, Janice M. DeGraziano, Roel M. Hermant, David Nicodem, Peter Craig, Gilbert R. Seely, Ronald A. Nieman

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Abstract

A porphyrin dyad designed to facilitate vectorial interporphyrin electron transfer has been synthesized and studied using steady-state and time-resolved absorption and emission spectroscopies. The dyad features a zinc tetraarylporphyrin bearing electron-donating substituents linked by an amide bond to a free base porphyrin carrying electron-withdrawing groups. Excitation of the zinc porphyrin moiety in dichloromethane solution is followed by singlet energy transfer to the free base and concurrent electron transfer to the same moiety to yield a charge-separated state. The free base first excited singlet state decays by accepting an electron from the zinc porphyrin to form the same charge-separated state. Similar results are observed in butyronitrile. Transient absorption studies in butyronitrile verify the formation of a short-lived (8 ps) charge-separated state from the porphyrin first excited singlet states. The results support the suggestion that fluorescence quenching in related porphyrin dyads and carotenoid-diporphyrin triads is due to photoinduced electron transfer, rather than some other decay process.

Original languageEnglish (US)
Pages (from-to)7926-7931
Number of pages6
JournalJournal of Physical Chemistry
Volume97
Issue number30
StatePublished - 1993

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Porphyrins
porphyrins
electron transfer
Electrons
Zinc
zinc
Excited states
Bearings (structural)
excitation
carotenoids
electrons
Methylene Chloride
Dichloromethane
Emission spectroscopy
decay
Carotenoids
Absorption spectroscopy
Amides
Energy transfer
amides

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Gust, D., Moore, T., Moore, A., Leggett, L., Lin, S., DeGraziano, J. M., ... Nieman, R. A. (1993). Photoinduced electron transfer in a porphyrin dyad. Journal of Physical Chemistry, 97(30), 7926-7931.

Photoinduced electron transfer in a porphyrin dyad. / Gust, Devens; Moore, Thomas; Moore, Ana; Leggett, Lana; Lin, Su; DeGraziano, Janice M.; Hermant, Roel M.; Nicodem, David; Craig, Peter; Seely, Gilbert R.; Nieman, Ronald A.

In: Journal of Physical Chemistry, Vol. 97, No. 30, 1993, p. 7926-7931.

Research output: Contribution to journalArticle

Gust, D, Moore, T, Moore, A, Leggett, L, Lin, S, DeGraziano, JM, Hermant, RM, Nicodem, D, Craig, P, Seely, GR & Nieman, RA 1993, 'Photoinduced electron transfer in a porphyrin dyad', Journal of Physical Chemistry, vol. 97, no. 30, pp. 7926-7931.
Gust, Devens ; Moore, Thomas ; Moore, Ana ; Leggett, Lana ; Lin, Su ; DeGraziano, Janice M. ; Hermant, Roel M. ; Nicodem, David ; Craig, Peter ; Seely, Gilbert R. ; Nieman, Ronald A. / Photoinduced electron transfer in a porphyrin dyad. In: Journal of Physical Chemistry. 1993 ; Vol. 97, No. 30. pp. 7926-7931.
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AU - Gust, Devens

AU - Moore, Thomas

AU - Moore, Ana

AU - Leggett, Lana

AU - Lin, Su

AU - DeGraziano, Janice M.

AU - Hermant, Roel M.

AU - Nicodem, David

AU - Craig, Peter

AU - Seely, Gilbert R.

AU - Nieman, Ronald A.

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N2 - A porphyrin dyad designed to facilitate vectorial interporphyrin electron transfer has been synthesized and studied using steady-state and time-resolved absorption and emission spectroscopies. The dyad features a zinc tetraarylporphyrin bearing electron-donating substituents linked by an amide bond to a free base porphyrin carrying electron-withdrawing groups. Excitation of the zinc porphyrin moiety in dichloromethane solution is followed by singlet energy transfer to the free base and concurrent electron transfer to the same moiety to yield a charge-separated state. The free base first excited singlet state decays by accepting an electron from the zinc porphyrin to form the same charge-separated state. Similar results are observed in butyronitrile. Transient absorption studies in butyronitrile verify the formation of a short-lived (8 ps) charge-separated state from the porphyrin first excited singlet states. The results support the suggestion that fluorescence quenching in related porphyrin dyads and carotenoid-diporphyrin triads is due to photoinduced electron transfer, rather than some other decay process.

AB - A porphyrin dyad designed to facilitate vectorial interporphyrin electron transfer has been synthesized and studied using steady-state and time-resolved absorption and emission spectroscopies. The dyad features a zinc tetraarylporphyrin bearing electron-donating substituents linked by an amide bond to a free base porphyrin carrying electron-withdrawing groups. Excitation of the zinc porphyrin moiety in dichloromethane solution is followed by singlet energy transfer to the free base and concurrent electron transfer to the same moiety to yield a charge-separated state. The free base first excited singlet state decays by accepting an electron from the zinc porphyrin to form the same charge-separated state. Similar results are observed in butyronitrile. Transient absorption studies in butyronitrile verify the formation of a short-lived (8 ps) charge-separated state from the porphyrin first excited singlet states. The results support the suggestion that fluorescence quenching in related porphyrin dyads and carotenoid-diporphyrin triads is due to photoinduced electron transfer, rather than some other decay process.

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