Stabilization of Acenes: “Geländer”‐Pentacenes

We report soluble tetrakis‐biphenylyl substituted pentacenes comprised of sp2 carbons and synthesized from pentacene‐5,7,12,14‐tetraone. Intramolecular Yamamoto coupling of two tetrakis(chlorobiphenylyl)pentacenes yields helical, doubly wrapped pentacenes, in which the quaterphenylene units solubilize the pentacenes and shield their central anthracene units to an unprecedented degree. The criss‐cross‐bridged pentacenes resist (photo)oxidation, Diels–Alder reactions and are much less reactive than TIPS‐ethynylated pentacene. Extension of this concept might provide access to the larger acenes. A convenient three‐step synthesis, starting from commercially available pentacenetetraone, gives helical, doubly quaterphenylene wrapped pentacenes. The “Geländer” architecture effectively shields the acene backbones—the para‐quaterphenylene derivative displays unique stability with respect to photoxodiation and Diels–Alder reaction with PTAD or fullerene.