Series of 1,8-diazabenzopyrenes and 1,7-diazaperylenes with thienyl or 4-(phenylamino)phenyl groups were designed and synthesized by a one-pot process from the functionalized terminal alkynes and either 1,4- or 1,5-diiodoanthraquinones in order to investigate the effect of extending π-conjugation at the 2,7- and 2,8-positions on the optical and electrochemical properties. The substances synthesized were characterized by X-ray analysis, cyclic voltammetry, UV–vis and luminescence spectroscopy. Energies and spin-densities of frontier molecular orbitals were calculated by DFT. Practically planar crystal structures of 1,8-diazabenzopyrene and 1,7-diazaperylene with thienyl groups were confirmed by X-ray diffraction data. Solid-state luminescence was obtained for the synthesized substances in drop-casted films and in 1,4-dioxane/water mixtures.