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Title: Photoinduced electron transfer in a porphyrin dyad

Abstract

A prophyrin 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 tetraaylporphyrin 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. 17 refs., 8 refs.

Authors:
; ; ; ; ; ; ; ; ; ;  [1]
  1. Arizona State Univ., Tempe (United States)
Publication Date:
OSTI Identifier:
5930390
DOE Contract Number:  
FG05-87ER75361; FG02-88ER13969
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry; (United States)
Additional Journal Information:
Journal Volume: 97:30; Journal ID: ISSN 0022-3654
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ZINC COMPLEXES; ELECTRON TRANSFER; FLUORESCENCE; METHYLENE CHLORIDE; NITRILES; PHOTOSYNTHESIS; PORPHYRINS; RADICALS; SPECTROSCOPY; VOLTAMETRY; CARBOXYLIC ACIDS; CHEMICAL REACTIONS; COMPLEXES; HETEROCYCLIC ACIDS; HETEROCYCLIC COMPOUNDS; LUMINESCENCE; ORGANIC ACIDS; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PHOTOCHEMICAL REACTIONS; SYNTHESIS; 140505* - Solar Energy Conversion- Photochemical, Photobiological, & Thermochemical Conversion- (1980-); 400500 - Photochemistry

Citation Formats

Gust, D, Moore, T A, Moore, A L, Leggett, L, Lin, S, DeGraziano, J M, Hermant, R M, Nicodem, D, Craig, P, Seely, G R, and Nieman, R A. Photoinduced electron transfer in a porphyrin dyad. United States: N. p., 1993. Web. doi:10.1021/j100132a021.
Gust, D, Moore, T A, Moore, A L, Leggett, L, Lin, S, DeGraziano, J M, Hermant, R M, Nicodem, D, Craig, P, Seely, G R, & Nieman, R A. Photoinduced electron transfer in a porphyrin dyad. United States. https://doi.org/10.1021/j100132a021
Gust, D, Moore, T A, Moore, A L, Leggett, L, Lin, S, DeGraziano, J M, Hermant, R M, Nicodem, D, Craig, P, Seely, G R, and Nieman, R A. Thu . "Photoinduced electron transfer in a porphyrin dyad". United States. https://doi.org/10.1021/j100132a021.
@article{osti_5930390,
title = {Photoinduced electron transfer in a porphyrin dyad},
author = {Gust, D and Moore, T A and Moore, A L and Leggett, L and Lin, S and DeGraziano, J M and Hermant, R M and Nicodem, D and Craig, P and Seely, G R and Nieman, R A},
abstractNote = {A prophyrin 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 tetraaylporphyrin 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. 17 refs., 8 refs.},
doi = {10.1021/j100132a021},
url = {https://www.osti.gov/biblio/5930390}, journal = {Journal of Physical Chemistry; (United States)},
issn = {0022-3654},
number = ,
volume = 97:30,
place = {United States},
year = {1993},
month = {7}
}