Dibenzothienopyrrolo[3,2-b]pyrrole: The Missing Member of the Thienoacene Family

Dibenzothienopyrrolo[3,2-b]pyrrole and the corresponding bis(S,S-dioxide) were synthesized by using a concise synthetic strategy. Despite the presence of six fused aromatic rings, π-expanded pyrrolo[3,2-b]pyrroles of this type absorb and emit at relatively short wavelengths, which reflects inefficient π conjugation due to the angular arrangement of the aromatic rings. They exhibit interesting and complex electrochemical behavior, which highlights their potential in organic electronics. Both heteroacenes undergo two-stage oxidation while retaining the independence of each 1-phenyl-1H-[1]benzothieno[3,2-b]pyrrole, which was proved by in situ electron spin resonance measurements. Interestingly, electrochemically generated dicationdiradicals are not only distributed over the pyrrolo[3,2-b]pyrrole scaffold, but also over the phenyl substituents located on nitrogen atoms.