Extended O‐Doped Polycyclic Aromatic Hydrocarbons

The synthesis of O‐doped benzorylenes, in which peripheral carbon atoms have been replaced by oxygen atoms, has been achieved for the first time. This includes key high‐yielding ring‐closure steps which, through intramolecular C−O bond formation, allow stepwise planarization of oligonaphthalenes. Single‐crystal X‐ray diffraction showed that the tetraoxa derivative forms remarkable face‐to‐face π–π stacks in the solid state, a favorable solid‐state arrangement for organic electronics.