Driving force and electronic coupling effects on photoinduced electron transfer in a fullerene-based molecular triad

Jeffrey L. Bahr, Darius Kuciauskas, Paul A. Liddell, Ana L Moore, Thomas A Moore, John Devens Gust

Research output: Contribution to journalArticle

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Abstract

Tuning thermodynamic driving force and electronic coupling through structural modifications of a carotene (C) porphyrin (P) fullerene (C60) molecular triad has permitted control of five electron and energy transfer rate constants and two excited state lifetimes in order to prepare a high-energy charge-separated state by photoinduced electron transfer with a quantum yield of essentially unity (≥96%). Excitation of the porphyrin moiety of C-P-C60 is followed by a combination of photoinduced electron transfer to give C-P·+-C60·- and singlet-singlet energy transfer to yield C-P-1C60. The fullerene excited state accepts an electron from the porphyrin to also generate C-P·+-C60·-. Overall, this initial state is formed with a quantum yield of 0.97. Charge shift from the carotenoid to yield C·+-P-C60·- is at least 60 times faster than recombination of C-P·+-C60·-, leading to the overall quantum yield near unity for the final state. Formation of a similar charge-separated species from the zinc analog of the triad with a yield of 40% is also observed. Charge recombination of C·+-P-C60·- in 2-methyltetrahydrofuran yields the carotenoid triplet state, rather than the ground state. Comparison of the results for this triad with those for related triads with different structural features provides information concerning the effects of driving force and electronic coupling on each of the electron transfer steps.

Original languageEnglish
Pages (from-to)598-611
Number of pages14
JournalPhotochemistry and Photobiology
Volume72
Issue number5
DOIs
Publication statusPublished - Nov 1 2000

Fingerprint

Fullerenes
fullerenes
electron transfer
porphyrins
Electrons
Porphyrins
Quantum yield
Carotenoids
carotenoids
electronics
Energy Transfer
unity
Excited states
Energy transfer
energy transfer
Genetic Recombination
excitation
carotene
atomic energy levels
Thermodynamics

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)
  • Biochemistry
  • Biophysics

Cite this

Driving force and electronic coupling effects on photoinduced electron transfer in a fullerene-based molecular triad. / Bahr, Jeffrey L.; Kuciauskas, Darius; Liddell, Paul A.; Moore, Ana L; Moore, Thomas A; Gust, John Devens.

In: Photochemistry and Photobiology, Vol. 72, No. 5, 01.11.2000, p. 598-611.

Research output: Contribution to journalArticle

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