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- W3005853008 abstract "The spectroscopic properties and dynamics of the excited states of two different synthetic analogues of peridinin were investigated as a function of solvent polarity using steady-state absorption, fluorescence, and ultrafast time-resolved optical spectroscopy. The analogues are denoted S-1- and S-2-peridinin and differ from naturally occurring peridinin in the location of the lactone ring and its associated carbonyl group, known to be obligatory for the observation of a solvent dependence of the lifetime of the S₁ state of carotenoids. Relative to peridinin, S-1- and S-2-peridinin have their lactone rings two and four carbons more toward the center of the π-electron system of conjugated carbon–carbon double bonds, respectively. The present experimental results show that as the polarity of the solvent increases, the steady-state spectra of the molecules broaden, and the lowest excited state lifetime of S-1-peridinin changes from ∼155 to ∼17 ps which is similar to the magnitude of the effect reported for peridinin. The solvent-induced change in the lowest excited state lifetime of S-2-peridinin is much smaller and changes only from ∼90 to ∼67 ps as the solvent polarity is increased. These results are interpreted in terms of an intramolecular charge transfer (ICT) state that is formed readily in peridinin and S-1-peridinin, but not in S-2-peridinin. Quantum mechanical computations reveal the critical factors required for the formation of the ICT state and the associated solvent-modulated effects on the spectra and dynamics of these molecules and other carbonyl-containing carotenoids and polyenes. The factors are the magnitude and orientation of the ground- and excited-state dipole moments which must be suitable to generate sufficient mixing of the lowest two excited singlet states." @default.
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- W3005853008 date "2012-01-01" @default.
- W3005853008 modified "2023-09-23" @default.
- W3005853008 title "Effect of Molecular Symmetry on the Spectra and Dynamics of the Intramolecular Charge Transfer (ICT) State of Peridinin" @default.
- W3005853008 hasPublicationYear "2012" @default.
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