We disclose π-expanded pyracylenes and their cationic species comprising 7-membered rings. The compounds were synthesized by stepwise oxidative cyclodehydrogenation to monitor the effect of successive cyclization on the structural and optoelectronic properties. As shown by X-ray crystallography the complete cyclization leads to a boat-shaped scaffold featuring negative curvature provided by the 7-membered ring. The embedded tropone unit enabled the convenient generation of a stabilized …