Photoinduced Electron Transfer and Hole Migration Along Copolymer of Vinylbenzenepyrrolidinofullerene[60] and N-Vinylcarbazole

Abstract

Photoinduced electron-transfer and hole-migration processes for newly prepared copolymers of C60 and N-vinylcarbazole (VCz) with the several compositions have been investigated using time-resolved fluorescence and absorption methods. Shortening of fluorescence lifetime of the C60 moiety in PVCz-C60 was observed, suggesting that the charge-separation takes place via the excited singlet state of C60; the rate constants of the charge-separation were evaluated to be larger than 10(9) S(-1) in polar solvents. In the nanosecond transient absorption spectra in the visible and near-IR regions obtained by excitation of the C60 moiety, the generation of PVCz(*+)-C60(*-) was confirmed. The time profiles of these radical ions showed slow decay continuing more than 800 micros in polar solvents. From the simulations of the decay curves on the basis of the proposed kinetic model, in which the charge-recombination takes place competitively with hole-migration, the rate parameters have been evaluated; i.e., the rate constant of hole migration was evaluated to be 5 x 10(7) s(-1), which was 50 times faster than that of the charge-recombination (ca. 10(6) s(-1)) in polar solvent. The charge-recombination takes place after hole migration among 200-300 Cz units along the PVCz chain in PVCz-C60.