Effect of Azulene Substitution on Some Photophysical Properties of Triphenyl and Tritolyl Corroles
Abstract
Azulene, when attached to another system such as corrole, brings significant changes in the electronic structure by changing the dipole moment and by participating in π-conjugation. This may impact the optical properties and charge-transfer mechanisms. Literature suggests that no such effect has yet been explored for corroles. In this work, we present a detailed computational study about the effect of azulene attachment on absorption (one- and two-photon) and charge-transfer in two experimentally studied corroles, i.e., triphenyl corrole (TPC) and tritolyl corrole (TTC) where the three meso-positions of the corrole ring are substituted by phenyl and tolyl groups respectively. We employed density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods in conjugation with integral equation formalism polarizable continuum model (IEFPCM) solvent model to study the said properties. Additionally, we employed a three-state model to reveal the most contributing transition dipole moment(s) and the effect of their relative orientation on the optical properties.