Excited state electron transfer in A2 and A2B2 functionalized zinc porphyrins carrying rigid and flexible β-pyrrole π-extended substituents

Abstract

Optical absorption and emission, electrochemical, and photochemical properties of peripherally functionalized with flexible and rigid [Formula: see text]-extended substituents on A2 and A2B2 type zinc porphyrins is investigated. The significance of rigid [Formula: see text]-substituents over flexible ones in governing the spectral properties is unraveled. Flexible [Formula: see text]-substituents on the porphyrin ring caused appreciable spectral broadening compared to porphyrin carrying rigid [Formula: see text]-substituents. Further, supramolecular dyads are formed by coordinating phenyl imidazole functionalized fullerene, C[Formula: see text]Im. The calculated binding constants for the 1:1 complexes is in the order of 2–7 × 105 M[Formula: see text] suggesting stable complex formation. Free-energy calculations performed according to the Rehm–Weller approach suggested possibility of excited state electron transfer in these dyads. Femtosecond transient absorption studies of the dyads performed in [Formula: see text]-dichlorobenzene showed evidence of occurrence of electron transfer from the singlet-excited state that was in competition with the intersystem crossing process to populate the triplet-excited state of porphyrins.