Symmetry control of radiative decay in linear polyenes: Low barriers for isomerization in the S1 state of hexadecaheptaene

Ronald L. Christensen, Mary Grace Ignacio Galinato, Emily F. Chu, Ritsuko Fujii, Hideki Hashimoto, Harry A. Frank

Research output: Contribution to journalArticle

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Abstract

The room temperature absorption and emission spectra of the 4-cis and all-trans isomers of 2,4,6,8,10,12,14-hexadecaheptaene are almost identical, exhibiting the characteristic dual emissions S1→S0 (21Ag- → 11Ag -) and S2→S0 (11B U+ → 11Ag-) noted in previous studies of intermediate length polyenes and carotenoids. The ratio of the S1→S0 and S2→S0 emission yields for the cis isomer increases by a factor of ∼15 upon cooling to 77 K in n-pentadecane. In contrast, for the trans isomer this ratio shows a 2-fold decrease with decreasing temperature. These results suggest a low barrier for conversion between the 4-cis and all-trans isomers in the S1 state. At 77 K, the cis isomer cannot convert to the more stable all-trans isomer in the 21Ag- state, resulting in the striking increase in its S1→S0 fluorescence. These experiments imply that the S1 states of longer polyenes have local energy minima, corresponding to a range of conformations and isomers, separated by relatively low (2-4 kcal) barriers. Steady state and time-resolved optical measurements on the S1 states in solution thus may sample a distribution of conformers and geometric isomers, even for samples represented by a single, dominant ground state structure. Complex S1 potential energy surfaces may help explain the complicated S2→S 1 relaxation kinetics of many carotenoids. The finding that fluorescence from linear polyenes is so strongly dependent on molecular symmetry requires a reevaluation of the literature on the radiative properties of all-trans polyenes and carotenoids.

Original languageEnglish (US)
Pages (from-to)1769-1775
Number of pages7
JournalJournal of the American Chemical Society
Volume129
Issue number6
DOIs
StatePublished - Feb 14 2007

Fingerprint

Polyenes
Isomerization
Isomers
Carotenoids
Fluorescence
Temperature
Potential energy surfaces
Ground state
Conformations
Cooling
Kinetics

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Christensen, Ronald L. ; Galinato, Mary Grace Ignacio ; Chu, Emily F. ; Fujii, Ritsuko ; Hashimoto, Hideki ; Frank, Harry A. / Symmetry control of radiative decay in linear polyenes : Low barriers for isomerization in the S1 state of hexadecaheptaene. In: Journal of the American Chemical Society. 2007 ; Vol. 129, No. 6. pp. 1769-1775.
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Symmetry control of radiative decay in linear polyenes : Low barriers for isomerization in the S1 state of hexadecaheptaene. / Christensen, Ronald L.; Galinato, Mary Grace Ignacio; Chu, Emily F.; Fujii, Ritsuko; Hashimoto, Hideki; Frank, Harry A.

In: Journal of the American Chemical Society, Vol. 129, No. 6, 14.02.2007, p. 1769-1775.

Research output: Contribution to journalArticle

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T2 - Low barriers for isomerization in the S1 state of hexadecaheptaene

AU - Christensen, Ronald L.

AU - Galinato, Mary Grace Ignacio

AU - Chu, Emily F.

AU - Fujii, Ritsuko

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AU - Frank, Harry A.

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N2 - The room temperature absorption and emission spectra of the 4-cis and all-trans isomers of 2,4,6,8,10,12,14-hexadecaheptaene are almost identical, exhibiting the characteristic dual emissions S1→S0 (21Ag- → 11Ag -) and S2→S0 (11B U+ → 11Ag-) noted in previous studies of intermediate length polyenes and carotenoids. The ratio of the S1→S0 and S2→S0 emission yields for the cis isomer increases by a factor of ∼15 upon cooling to 77 K in n-pentadecane. In contrast, for the trans isomer this ratio shows a 2-fold decrease with decreasing temperature. These results suggest a low barrier for conversion between the 4-cis and all-trans isomers in the S1 state. At 77 K, the cis isomer cannot convert to the more stable all-trans isomer in the 21Ag- state, resulting in the striking increase in its S1→S0 fluorescence. These experiments imply that the S1 states of longer polyenes have local energy minima, corresponding to a range of conformations and isomers, separated by relatively low (2-4 kcal) barriers. Steady state and time-resolved optical measurements on the S1 states in solution thus may sample a distribution of conformers and geometric isomers, even for samples represented by a single, dominant ground state structure. Complex S1 potential energy surfaces may help explain the complicated S2→S 1 relaxation kinetics of many carotenoids. The finding that fluorescence from linear polyenes is so strongly dependent on molecular symmetry requires a reevaluation of the literature on the radiative properties of all-trans polyenes and carotenoids.

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