Excited State Properties of Peridinin

Observation of a Solvent Dependence of the Lowest Excited Singlet State Lifetime and Spectral Behavior Unique among Carotenoids

James A. Bautista, Robert E. Connors, B. Bangar Raju, Roger G. Hiller, Frank P. Sharples, David Gosztola, Michael R Wasielewski, Harry A. Frank

Research output: Contribution to journalArticle

174 Citations (Scopus)

Abstract

The spectroscopic properties and dynamic behavior of peridinin in several different solvents were studied by steady-state absorption, fluorescence, and transient optical spectroscopy. The lifetime of the lowest excited singlet state of peridinin is found to be strongly dependent on solvent polarity and ranges from 7 ps in the strongly polar solvent trifluoroethanol to 172 ps in the nonpolar solvents cyclohexane and benzene. The lifetimes show no obvious correlation with solvent polarizability, and hydrogen bonding of the solvent molecules to peridinin is not an important factor in determining the dynamic behavior of the lowest excited singlet state. The wavelengths of emission maxima, the quantum yields of fluorescence, and the transient absorption spectra are also affected by the solvent environment. A model consistent with the data and supported by preliminary semiempirical calculations invokes the presence of a charge transfer state in the excited state manifold of peridinin to account for the observations. The charge transfer state most probably results from the presence of the lactone ring in the π-electron conjugation of peridinin analogous to previous findings on aminocoumarins and related compounds. The behavior of peridinin reported here is highly unusual for carotenoids, which generally show little dependence of the spectral properties and lifetimes of the lowest excited singlet state on the solvent environment.

Original languageEnglish
Pages (from-to)8751-8758
Number of pages8
JournalJournal of Physical Chemistry B
Volume103
Issue number41
Publication statusPublished - Oct 14 1999

Fingerprint

carotenoids
Carotenoids
Excited states
life (durability)
excitation
Charge transfer
Aminocoumarins
Fluorescence
charge transfer
Trifluoroethanol
fluorescence
peridinin
Quantum yield
Lactones
Cyclohexane
Benzene
conjugation
cyclohexane
Absorption spectra
polarity

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Bautista, J. A., Connors, R. E., Raju, B. B., Hiller, R. G., Sharples, F. P., Gosztola, D., ... Frank, H. A. (1999). Excited State Properties of Peridinin: Observation of a Solvent Dependence of the Lowest Excited Singlet State Lifetime and Spectral Behavior Unique among Carotenoids. Journal of Physical Chemistry B, 103(41), 8751-8758.

Excited State Properties of Peridinin : Observation of a Solvent Dependence of the Lowest Excited Singlet State Lifetime and Spectral Behavior Unique among Carotenoids. / Bautista, James A.; Connors, Robert E.; Raju, B. Bangar; Hiller, Roger G.; Sharples, Frank P.; Gosztola, David; Wasielewski, Michael R; Frank, Harry A.

In: Journal of Physical Chemistry B, Vol. 103, No. 41, 14.10.1999, p. 8751-8758.

Research output: Contribution to journalArticle

Bautista, James A. ; Connors, Robert E. ; Raju, B. Bangar ; Hiller, Roger G. ; Sharples, Frank P. ; Gosztola, David ; Wasielewski, Michael R ; Frank, Harry A. / Excited State Properties of Peridinin : Observation of a Solvent Dependence of the Lowest Excited Singlet State Lifetime and Spectral Behavior Unique among Carotenoids. In: Journal of Physical Chemistry B. 1999 ; Vol. 103, No. 41. pp. 8751-8758.
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