Issue 22, 2011

Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics

Abstract

Carotenoids containing a carbonyl group in conjugation with their polyene backbone are naturally-occurring pigments in marine organisms and are essential to the photosynthetic light-harvesting function in aquatic algae. These carotenoids exhibit spectral characteristics attributed to an intramolecular charge transfer (ICT) state that arise in polar solvents due to the presence of the carbonyl group. Here, we report the spectroscopic properties of the carbonyl carotenoid fucoxanthin in polar (methanol) and nonpolar (cyclohexane) solvents studied by steady-state absorption and femtosecond pump–probe measurements. Transient absorption associated with the optically forbidden S1 (21Ag) state and/or the ICT state were observed following one-photon excitation to the optically allowed S2 (11B+u) state in methanol. The transient absorption measurements carried out in methanol showed that the ratio of the ICT-to-S1 state formation increased with decreasing excitation energy. We also showed that the ICT character was clearly visible in the steady-state absorption in methanol based on a Franck–Condon analysis. The results suggest that two spectroscopic forms of fucoxanthin, blue and red, exist in the polar environment.

Graphical abstract: Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics

Article information

Article type
Paper
Submitted
17 Nov 2010
Accepted
25 Mar 2011
First published
06 May 2011

Phys. Chem. Chem. Phys., 2011,13, 10762-10770

Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics

D. Kosumi, T. Kusumoto, R. Fujii, M. Sugisaki, Y. Iinuma, N. Oka, Y. Takaesu, T. Taira, M. Iha, H. A. Frank and H. Hashimoto, Phys. Chem. Chem. Phys., 2011, 13, 10762 DOI: 10.1039/C0CP02568B

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