Perturbation of Electronic States and Energy Relaxation Dynamics in a Series of Phenylene Bridged ZnII Porphyrin Dimers

Abstract

We have investigated the perturbed electronic states and energy relaxation dynamics of a series of phenylene bridged ZnII porphyrin dimers to reveal the effects of phenylene bridges by using computational and time-resolved spectroscopic methods. The electronic states of ZnII porphyrin dimers are largely perturbed by the interchromophore interactions that can be controlled by the phenylene bridges; linking position and number of phenyl rings. On the basis of our observations, we can gain further insight into the dipole−dipole interactions and through-bond/through-space electronic exchange interactions between the neighboring porphyrin moieties, which provides a firm basis for further understanding the modification of photophysical properties caused by the phenylene bridge in multiporphyrin assemblies as artificial light-harvesting apparatus.