Twisted Polycyclic Arenes from Tetranaphthyldiphenylbenzenes by Controlling the Scholl Reaction with Substituents

Herein, we report two new types of twisted polycyclic arenes ( 2 a , b and 3 a , b ) with constitutionally isomeric π‐backbones, which are synthesized by controlling the Scholl reaction of 1,2,4,5‐tetra(naphth‐2‐yl)‐3,6‐diphenylbenzene ( 1 ) with properly positioned electron‐donating substituents. With a polycyclic backbone containing two [5]helicene and four [4]helicene moieties, 2 a and b are new members of multiple helicenes with interesting stereochemistries. The as‐synthesized 2 a and b are the twisted isomers, and thermal isomerization of twisted‐ 2 b results in anti‐ 2 b , a more stable stereoisomer. Both twisted‐ and anti‐ 2 b have been fully characterized, and the thermal isomerization of twisted‐ 2 b has been studied with ¹H NMR spectroscopy and DFT calculations. Compounds 3 a and b are new members of twistacenes, the benzannulated pentacene backbone of which exhibits an end‐to‐end twist as found from the crystal structure. Twisted‐ and anti‐ 2 b are also found to function as p‐type semiconductors in solution‐processed thin film transistors, whereas the thin films of 3 b appear insulating presumably due to the lack of π–π interactions.