Abstract The synthesis of three novel imidazolyl‐substituted sulfur‐containing heteroacenes is reported. These heteroacenes consisting of annelated benzo‐ and naphthothiophenes serve as precursors for the generation of open‐shell quinoid heteroacenes by oxidation with alkaline ferric cyanide. Spectroscopic and computational experiments support the formation of reactive open‐shell quinoids, which, however, quickly produce paramagnetic polymeric material.
