Octafunctionalized Biphenylenes: Molecular Precursors for Isomeric Graphene Nanostructures

A straightforward method for the octafunctionalization of biphenylene based on the [2+2]‐cycloaddition of an aryne intermediate has been developed. This enabled a “North–South” extension of biphenylene towards isomeric graphene nanoribbons composed of four‐, six‐, and eight‐membered rings. This procedure furthermore allowed an “East–West” expansion to [n]phenylenes with different lengths. For the fabrication of isomeric nanongraphenes, octaarylbiphenylenes decorated with phenyl, pyrenyl, and thieno substituents were prepared. The subsequent oxidative cyclodehydrogenation provided an expanded helicene as a model compound.