Linear Non-benzenoid Isomer of Acene Fusing Chrysene with Azulene Units

Abstract

Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have received considerable attention owing to their distinctive optical and electrical properties. Nevertheless, the synthesis and optoelectronic application of non-benzenoid PAHs remain challenging. Herein, we present a facile synthesis of linear non-benzenoid PAH with an armchair edge, diACh, by fusing chrysene with two azulene units. We systematically investigated the optical and electrical properties, which were also compared to its isomers, including benzenoid and non-benzenoid zigzag edge isomers. diACh exhibits global aromaticity, good planarity, and suitable highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels. The protonation of diACh in solution successively forms a stable tropylium cation and dication. Moreover, the neutral, cationic, and dicationic states of diACh can be transformed with remarkable reversibility during the protonation–deprotonation process, as confirmed by ultraviolet–visible absorptions, fluorescence spectra, 1H nuclear magnetic resonance, and theoretical calculations. Additionally, we fabricate p-type organic field-effect transistor (OFET) devices based on diACh with hole mobility up to 0.026 cm2 V–1 s–1, and we further develop OFET-based acid vapor sensors with good sensitivity, recyclability, and selectivity. These findings underscore the unique properties of linear non-benzenoid PAHs with an armchair edge engendered by the fusion of azulene with the acene backbone, showcasing prospective applications in organic optoelectronics.