Porphyrins bearing phenylenediamine pendant groups were synthesized to afford dimensionally oriented π-conjugated systems. The structural and electronic characteristics depend on the αααα and αβαβ atropisomers. In the fluorescence emission spectra, the emission from the porphyrin moiety was almost completely quenched. Zinc complexation of the αααα isomer with zinc(II) acetate led to the corresponding zinc complex.