Does the Intersystem Crossing Rate of β-Iodinated Phosphorus Corrole Depend on Iodine Numbers and/or Positions?

The heavy-atom effect is known to enhance the intersystem crossing (ISC) in organic molecular systems. Effects of iodine numbers and positions on the ISC rate of a few meso-difluorophenyl substituted β-iodinated phosphorus corroles (PCs) with axially ligated fluorine atoms (mI-FPC; m = 1-4) are studied using a time-dependent optimally tuned range-separated hybrid. Solvent effects are accounted for through a polarizable continuum model with a toluene dielectric. Calculations suggest similar thermodynamic stability for all mI-FPCs and also reproduce the experimentally measured 0-0 energies for some of the freebase phosphorus corrole (FPC) systems studied here. Importantly, our results reveal that all mI-FPCs display 10 times larger ISC rate (∼109 s-1) than the fluorescence rate (∼108 s-1), and the higher ISC rate stems from the improved spin-orbit coupling (SOC) introduced by lighter heteroatoms like central P and biaxial F rather than the I heavy-atom effect. However, an enhanced SOC is found with increasing I content for El-Sayed forbidden ISC channels. Research findings reported in this study unveil the impact of light heteroatoms and heavy atoms in promoting ISC in several iodinated PCs, which help in designing visible-light-driven efficient triplet photosensitizers.