Effect of meso-pentafluorophenyl group on two-photon absorption in heterocorroles and heterocorrins

Owing to their high reactivity, the meso-positions of corroles and corrins are usually protected by some bulky groups. These groups in addition to the said purpose may also affect the photophysical properties of such systems. However, there is no systematic study in the literature exploring this effect. In this work, we target to answer how the meso-substitution affects the photophysical properties in some heterocorroles and heterocorrins. We considered one of the commonly used substitutions, i.e., pentafluorophenyl (-PFPh), at meso positions of 26 heterocorroles and heterocorrins. We employed the state-of-the-art CC2 method in conjunction with resolution-of-identity approximation to study the charge-transfer and one- and two-photon absorption in these systems. It is further explored using a four-state model that helps in understanding the contribution of various transition dipole moments and their relative orientation. At the end, we also investigated the effect of other substitutions such as -CH3, -CF3, -C2H3, -OMe, -phenyl, and -tolyl on two-photon activity.