Photoinduced Electron Transfer and Hole Migration Along Copolymer of Vinylbenzenepyrrolidinofullerene and N-Vinylcarbazole
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 109 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•+−C•−60was confirmed. The time profiles of these radical ions showed slow decay continuing more than 800 s 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 × 107 S−1, which was 50 times faster than that of the charge-recombination (ca. 106 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.
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Document Type: Research Article
Publication date: 2007-04-01
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