Versatile Colorant Syntheses by Multiple Condensations of Acetyl Anilines with Perylene Anhydrides

We report a key step forward in rylene chemistry: the transformation of rylenes into novel chromophore families. The imidization of rylene anhydrides with 2‐acetyl anilines could be controlled by the choice of the solvent, thus causing a transformation into either a 4‐hydroxyquinoline (4‐HQ) or a 4‐oxoquinoline (4‐OQ) unit. The 4‐OQ motif contains an aminoenone group formed by intramolecular aldol condensation and is the first vinylogous rylene imide. The concept of vinylogy was further developed by utilizing 2,6‐diacetyl aniline leading to an 3a‐aza‐1,6‐phenalenedione‐extended rylene skeleton fully embracing the nitrogen atom. By functionalization of the aminoenone motifs, for example, malononitrile addition at the carbonyl groups, the optical and electronic properties could be further tuned. Color control: Novel π‐extended naphthalenes and perylenes containing 3a‐aza‐1,6‐phenalenedione‐, 4‐oxoquinoline‐, or 4‐hydroxyquinoline‐based chromophores were synthesized by a facile imidization of acetyl anilines with anhydrides and intramolecular aldol condensation. They show a strong red shift of the absorption bands relative to the parent imides, as well as fluorescence in the visible/NIR range.