Dinaphthobenzo[1,2:4,5]dicyclobutadiene: Antiaromatic and Orthogonally Tunable Electronics and Packing

Abstract

Abstract Polycyclic conjugated hydrocarbons containing antiaromatic four‐membered cyclobutadienoids (CDB) are of great fundamental and technical interest. However, their challenging synthesis has hampered the exploration and understanding of such systems. Reported herein is a modular and efficient synthesis of novel CBD‐containing acene analogues, dinaphthobenzo[1,2:4,5]dicyclobutadiene (DNBDCs), with orthogonally tunable electronic properties and molecular packing. The design also features strong antiaromaticity of the CBD units, as revealed by nucleus‐independent chemical shift and anisotropy of the induced current density calculations, as well as X‐ray crystallography. Tuning the size of silyl substituents resulted in the most favorable “brick‐layer” packing for triisobutylsilyl‐DNBDC and a charge mobility of up to 0.52 cm 2 V −1 s −1 in field‐effect transistors.