Effects of the Structural Rigidity of Polymethine Dye Molecules on Quenching of Their Photoluminescence by an Electric Field and Charge Photogeneration in Poly(N-epoxypropylcarbazole)

For photoconducting poly(N-epoxypropylcarbazole) films doped with cationic polymethine dyes used as an example, it was found that an increase in dye molecular rigidity increased the photoconductivity of the films in the region of dye absorption, quenching effect of an electric field on photoluminescence, and concentration ratio of photogenerated triplet electron–hole pairs to singlet pairs. The effects were enhanced by an increase in the quantum energy of excitation light. The results are explained by a decrease in the dissipation rate of the electronic excitation energy of dye molecules upon growing their rigidity, which accelerates singlet–triplet intersystem crossing in the photogenerated electron–hole pairs via the spin–lattice relaxation mechanism.