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Abstract
The ultrafast internal conversion (IC) dynamics of aldehyde-substituted apocarotenoids (n'-apo-beta-caroten-n'-als with n=4, 8 and 12) have been investigated in a systematic variation of conjugation length and solvent polarity using time-resolved femtosecond transient absorption spectroscopy. After excitation to the S2 state with different excess energies, the subsequent intramolecular dynamics were investigated at several probe wavelengths covering the S0-->S2 and S1/ICT-->Sn absorption bands. Time constants tau1 for the internal conversion process S1/ICT-->S0 of 4'-apo-beta-caroten-4'-al and 8'-apo-beta-caroten-8'-al have been newly measured. We compared these results with our earlier measurements for 12'-apo-beta-caroten-12'-al (D.A. Wild, K. Winkler, S. Stalke, K. Oum, T. Lenzer Phys. Chem. Chem. Phys. 2006, 8, 2499). In the case of the aldehyde with the longest conjugation (4'-apo-beta-caroten-4'-al), tau1 is almost independent of solvent polarity (4-5 ps), whereas a significant reduction of tau1 from 22.7 to 8.6 ps for the shorter 8'-apo-beta-caroten-8'-al and an even more pronounced reduction from 220 to 8.0 ps for 12'-apo-beta-caroten-12'-al were observed when the solvent medium was changed from n-hexane to methanol, respectively. In n-hexane, tau1 of the apocarotenals is strongly dependent on the conjugation length and this can be well understood in terms of an energy gap law description where the S1-S0 energy differences were estimated from their steady-state fluorescence spectra. In highly polar solvents, the IC to S0 is very fast, irrespective of the conjugation length. This is probably due to the stabilization of an intramolecular charge transfer (ICT) state in 12'-apo-beta-caroten-12'-al and 8'-apo-beta-caroten-8'-al. In the case of 4'-apo-beta-caroten-4'-al, such an influence of an ICT state is presumably less important than for the other two apocarotenals.
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