A correlation between N–C bond formation and CC bond breaking is constructed from the structures of a family of peri-naphthalenes with a second set of peri substituents.

n–π* interactions between naphtholate O anions and carbonyl groups are determined to be shorter than in corresponding naphthols by X-ray crystallography, and lead to cyclisations with long O–C bonds when the carbonyl group is replaced by a strongly electron deficient alkene.

1,5-Bis(dimethylamino)naphthalene can be oxidized directly to a dication or a cation derived from an acridino-acridine, the former stabilised by two dimethyliminium substituents, while the latter has a dimethylated nitrogen in the ring system.