Excited State Dynamics of Selected All-trans C40 Xanthophyll Carotenoids
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Abstract
We investigated the excited state dynamics of selected all-trans C40 xanthophyll carotenoids by ultrafast pump-supercontinuum probe (PSCP) spectroscopy in the spectral range 350–770 nm upon photoexcitation by a femtosecond laser (ca. 80 fs pulse length) near 500 nm in acetone. The following carotenoids were selected considering a systematic variation of the number and position of carbonyl (CO) and hydroxyl (OH) functional groups on the β-ionone rings and the change of the effective conjugation length of the polyene system: β-cryptoxanthin (1), echinenone (2), 3-hydroxyechinenone (3), 3′-hydroxyechinenone (4), canthaxanthin (5), adonirubin (6) and astaxanthin (7). The carotenoids featuring an increasing conjugation length, for example, (1), (3) and (6), showed a systematically shorter S1 lifetime of 8.7, 6.2 and 4.7 ps, respectively. Carotenoids with OH groups adjacent to a CO group showed slightly broader steady-state and transient absorption bands, but the influence on the S1 lifetime was minor compared to the case of CO substitution. Moreover, in all cases we observed clearly visible “S* signals”, namely a longer-lived characteristic S0 → S2 red-edge absorption and a negative signal in the S0 → S2 bleach region. This spectral signature is assigned to highly vibrationally excited molecules in the ground electronic state S0* which are generated by internal conversion from S1. The S0* species cool with a time constant of 9.2–9.6 ps in the case of the keto-substituted carotenoids (2)–(7), whereas we obtain a larger value of 13.2 ps for (1) which does not have a keto group. Our findings are supported by results from a global kinetic analysis procedure.
Acknowledgement
We thank Hansgeorg Ernst and Bernd Schäfer from BASF SE for their valuable advice and for providing carotenoids for the PSCP experiments. We also thank Nikolaus P. Ernsting and J. Luis Pérez Lustres (Humboldt University Berlin, Germany) for their continuous support and advice.
©2015 Walter de Gruyter Berlin/Boston
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- Preface
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- Collisional Relaxation of NCN: An Experimental Study with Laser-Induced Fluorescence
- Reaction of Chlorine Molecules with Unsaturated Submicron Organic Particles
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