Investigation of the push–pull effects on β-functionalized zinc porphyrin coordinated to C60 donor–acceptor conjugates

Two novel β-functionalized push–pull zinc porphyrins with amine or phenyl push-groups and cyclic imide or carboxylic esters pull-groups have been newly synthesized for light energy harvesting applications. The ethynylphenyl spacers extended the conjugation of the porphyrin π-systems, as reflected by their red-shifted absorbance and fluorescence spectra. Computational studies performed at the B3LYP/6-31G* level indicated no steric hindrance between the porphyrin π-system and the substituents. The calculated HOMO and LUMO orbitals displayed significant delocalization in 1, where the electron density in the HOMO was localized over the push groups, whereas the LUMO was extended over the porphyrin π- and pull-groups. On the other hand, 2 did not display significant orbital segregation, which is attributed to its weaker push–pull character. Electrochemical studies revealed smaller HOMO–LUMO gaps for the push–pull zinc porphyrins. As a consequence of the push–pull effects, reduction in fluorescence intensity and...