We envisaged that if a similar helical structure could be synthesized more easily, we could obtain advanced molecules, the physical properties of which could be finely tuned by introducing substituents and/or switched by applying external stimuli. Herein, we report the first example of nitrogen (N)-centered helical heptalene 1 (Figure ), where the azaheptalene skeleton can be constructed by a palladiumcatalyzed one-pot reaction. Thanks to the electron-donating ablity of the central nitrogen atom, electrophilic bromination of 1 proceeds easily to produce mono-and dibrominated azaheptalene derivatives 2 and 3, and these azaheptalenes all undergo one-electron oxidation to give the corresponding radical cation species. Furthermore, due to the contiguous 6-7-7-6 ring system, these Ndoped heptalenes gain configurational stability, so that not only photophysical properties but also chiroptical properties can be controlled by an electric potential. Pentabenzoazaheptalene 1 was synthesized by a one-pot reaction (y. 82%) via Buchwald-Hartwig amination of 2,2'-dibromobiphenyl and 9H-tribenzo[b,d,f]azepine followed by the palladium-catalyzed C-C bond formation (Scheme 1). Due to the electron-donating nitrogen atom, selective bromination of 1 proceeded cleanly. By treatment of 1 with one equivalent of NBS and three equivalents of Br 2 , monoand dibrominated derivatives 2 and 3 were obtained in 53% and 86% yields, respectively. During these reactions, overbrominated compound was not found because of the lower contribution of HOMO on the benzene ring at the center of the molecule compared to the contributions of those on both sides (Figure ).