Indolo[2,3-a]carbazole-based heteroacenes containing thiadiazole units were synthesized. Compounds showed a sandwich herringbone packing in solid state with improved stability. The change in photophysical and electrochemical properties upon incorporation of an acceptor moiety (benzothiadazole) in a fused ring system was studied. The unsubstituted compound was electropolymerized to yield a stable polymer.