Abstract
Porphyrin complexes with appended electron accepting groups (EAGs), particularly at the β-pyrrolic position are known to have interesting optical properties. We have extended these studies to Zn(II) porphyrins with appended groups at the β-pyrrolic position bridged by a butadiene that include nitro, 1,3-diphenyl-barbituric acid, indolium and dinitrophenyl hydrazone. Resonance Raman spectroscopy, coupled with DFT methods, are used to determine the reorganized nature of the electronic structure. New electronic transitions are observed that are associated with the EAGs. Ruffled nickel(II) porphyrins in with the presence of thioether groups further distorts the electronic properties away from the four orbital model.