Subphthalocyanine (SubPc) and its benzo ring-removed analogue, subporphyrazine (SubPz), bearing 1,3-dithiole-2-one (S2CO) groups as a new class of substituents were synthesized. In addition to the perturbed optical properties due to the presence of electron-withdrawing S2CO units, the deep bowl-shaped structure of the SubPz derivative allowed concave–convex interaction to form a unique co-crystal structure with C60. Finally, using the reactivity of the peripheral S2CO units, S2CO-fused SubPc was successfully converted into tetrathiafulvalene (TTF)-annulated SubPc in a yield higher than that of the direct synthesis from a TTF-fused phthalonitrile.