Photoinduced electron transfer in a porphyrin dyad

Journal Article · Thu Jul 29 00:00:00 EDT 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100132a021· OSTI ID:5930390

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 ^[1]

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1. Arizona State Univ., Tempe (United States)

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.

• DOE Contract Number: FG05-87ER75361; FG02-88ER13969
• OSTI ID: 5930390
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 97:30; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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