Ultrafast Intramolecular Energy Relaxation Dynamics of Benzoporphyrins: Influence of Fused Benzo Rings on Singlet Excited States

We have investigated the role of fused benzo rings on the electronic structures and intramolecular energy relaxation dynamics in a series of benzoporphyrins (Bp1, syn-Bp2, anti-Bp2, Bp3, and Bp4) by using time-resolved fluorescence measurements and theoretical calculations. Interestingly, even though anti- and syn-Bp2 have the same number of fused benzo rings, in the respective absorption spectra, anti-Bp2 shows an obvious splitting of B_x (Q_x) and B_y (Q_y) states, whereas syn-Bp2 exhibits degenerate B and Q bands. These features provide two dynamical models for the effect of the position of substituted benzo rings on the intramolecular energy relaxation dynamics. syn-Bp2 gives rise to similar intramolecular dynamics from the B state to the Q state in the case of ZnTPP having D_4h molecular symmetry. On the other hand, anti-Bp2 shows split B and Q bands in the order B_y > B_x > Q_x > Q_y, which leads a superimposition of the Q_x (0,0) and Q_y (1,0) bands. This overlap generates a strong coupling between these two states, which results in a direct internal conversion from B_x (0,0) to Q_y (0,0). This observation suggests that the anti-type fused position of benzo rings leads to a new mechanism in internal conversion from the B to the Q state. On the basis of this work, further insight was obtained into the effect of fused benzo rings on the photophysical properties of benzoporphyrins, providing a detailed understanding of the structure−property relationship in a series of benzoporphyrins.