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The synthesis of O-doped benzorylenes, in which peripheral carbon atoms have been replaced by oxygen atoms, has been achieved for the first time.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.