Persistent Ambipolar Heptacenes and Their Redox Species

Abstract Sixfold TIPS‐ethynylation combined with fourfold bromination of the armchair edges furnishes a long‐lived, soluble heptacene; π‐extension via Stille coupling accesses a persistent tetrabenzononacene. Both types of acenes were stabilized best by double TIPS‐ethynylation on every other benzene ring. Tetrabromoheptacene is an ambipolar transistor material (up to 0.036 cm 2 V −1 s −1 n‐channel), which was corroborated by generation of its monoanion and monocation.