Azafullerene was prepared by addition of hydroxylamine to a cage-opened fullerendione derivative and subsequent PCl5 induced rearrangement processes. X-ray structures were obtained for the azafullerene and its azafulleroid precursor.

Open the cage if you dare: The azahomoazafullerene 1 was prepared from a tert‐butylperoxy‐substituted azafullerene derivative C59NBr(OOtBu)4. Singlet oxygen added to 1 to form an open‐cage azafullerene 2 with a ketoimide moiety on the rim of the orifice. The MALDI‐TOF mass spectrum of the product of the hydrolysis of 1 showed a clear signal for the diazafullerene C58N2 (see structure 3).