Triplet and singlet energy transfer in carotene-porphyrin dyads

Role of the linkage bonds

John Devens Gust, Thomas A Moore, Ana L Moore, Chelladurai Devadoss, Paul A. Liddell, Roel Hermant, Ronald A. Nieman, Lori J. Demanche, Janice M. DeGraziano, Isabelle Gouni

Research output: Contribution to journalArticle

154 Citations (Scopus)

Abstract

A series of carotenoporphyrin dyad molecules in which the carotenoid is covalently linked to a tetraarylporphyrin at the ortho, meta, or para position of a meso aromatic ring has been prepared, and the molecules have been studied using steady-state and transient fluorescence emission, transient absorption, and 1H NMR methods. Triplet-triplet energy transfer from the porphyrin moiety to the carotenoid has been observed, as has singlet-singlet energy transfer from the carotenoid polyene to the porphyrin. In addition, the carotenoid quenches the fluorescence of the attached porphyrin by a mechanism which increases internal conversion. The rates of all three of these processes are slower for the meta isomer than for the corresponding ortho and para molecules. Analysis of the data suggests that the triplet-triplet energy transfer is mediated by a through-bond (superexchange) mechanism involving the π-electrons of the linkage bonds, rather than a direct, through-space coupling of the chromophores. The same appears to be true for the process leading to enhanced internal conversion. The results are consistent with a role for the through-bond mechanism in the singlet-singlet energy transfer as well. Simple Hückel molecular orbital calculations are in accord with the proposed through-bond process.

Original languageEnglish
Pages (from-to)3590-3603
Number of pages14
JournalJournal of the American Chemical Society
Volume114
Issue number10
Publication statusPublished - May 6 1992

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Energy Transfer
Porphyrins
Carotenoids
Energy transfer
Molecules
Fluorescence
Polyenes
Orbital calculations
Molecular orbitals
Chromophores
Isomers
Nuclear magnetic resonance
Electrons

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Triplet and singlet energy transfer in carotene-porphyrin dyads : Role of the linkage bonds. / Gust, John Devens; Moore, Thomas A; Moore, Ana L; Devadoss, Chelladurai; Liddell, Paul A.; Hermant, Roel; Nieman, Ronald A.; Demanche, Lori J.; DeGraziano, Janice M.; Gouni, Isabelle.

In: Journal of the American Chemical Society, Vol. 114, No. 10, 06.05.1992, p. 3590-3603.

Research output: Contribution to journalArticle

Gust, JD, Moore, TA, Moore, AL, Devadoss, C, Liddell, PA, Hermant, R, Nieman, RA, Demanche, LJ, DeGraziano, JM & Gouni, I 1992, 'Triplet and singlet energy transfer in carotene-porphyrin dyads: Role of the linkage bonds', Journal of the American Chemical Society, vol. 114, no. 10, pp. 3590-3603.
Gust, John Devens ; Moore, Thomas A ; Moore, Ana L ; Devadoss, Chelladurai ; Liddell, Paul A. ; Hermant, Roel ; Nieman, Ronald A. ; Demanche, Lori J. ; DeGraziano, Janice M. ; Gouni, Isabelle. / Triplet and singlet energy transfer in carotene-porphyrin dyads : Role of the linkage bonds. In: Journal of the American Chemical Society. 1992 ; Vol. 114, No. 10. pp. 3590-3603.
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