Polarity of the Medium and Quenching of Fluorescence of Caratenoids and Phthalimides

The relation for the dependence of the rate of radiationless energy conversion of the S₁ state k_q on the polarity of the medium, obtained previously by the author, has been used to interpret the known literature data on the lifetime of the S₁ state of solutions of some caratenoids and phthalimides. It has been shown that in alcohols and water (normal and deuterated ones) the fluorescence quenching of 4-amino-, 4-methylamino-, and 4-dimethylamino-N-methylphthalimides (4AMP, 4MAMP, and 4DMAMP) as well as of peridinine in alcohols is due to H-bond formation. It has been established that a twofold increase in the number of amine atoms of hydrogen on passing from 4MAMP to 4AMP, as well as deuteration of solvents in the case of 4DMAMP, is followed by a decrease in k_q by a factor of 1.6 and 1.75, respectively. The mechanism of quenching in complexes formed with solvent molecules by means of the H-bond is discussed. It has been concluded that the quenching of fluorescence of phthalimides in such complexes is mainly due to the intersystem crossing initiated by the oscillations of the protons or deuterons of the H-bonds.