Modulation of internal conversion rate and nonlinear absorption in meso-tetraphenylporphyrins by donor/acceptor substitutes

Meso-tetraphenylporphyrin (TPP), (meso-tetrakis(4-cyanophenyl)porphyrin [TPP(CN)4)] and (meso-tetrakis(4-methoxyphenyl)porphyrin [TPP(OMe)4]) are synthesized. The donor methoxy substitute (OMe) and acceptor cyano substitute (CN) are introduced into TPP in order to examine their influence on the photophysical properties of TPP. The nonlinear absorption properties of these three porphyrins are studied using open-aperture Z-scan and time-resolved pump-probe techniques in picosecond and nanosecond regimes, and the results are elucidated successfully by a five-level model. As compared to TPP, TPP(OMe)4 exhibits an accelerated internal conversion from S1 to S0 state (0.02 ns), and S1 to T1 state (0.03 ns). Moreover, a changeover from saturable absorption to reverse saturable absorption is observed in TPP(OMe)4 in the ps regime. Whereas the nonlinear absorption behavior of TPP(CN)4 is similar to that of TPP. The results imply that these two substituents, especially the OMe group, could modulate the photophysical properties of TPP, which may provide a useful option for porphyrin-related applications.