Ren Peng, Chen Liangliang, Sun Chunlin, Hua Xinqiang, Luo Nan, Fan Baojin, Chen Pinyu, Shao Xiangfeng, Zhang Hao-Li, Liu Zitong
State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Special Function Materials and Structure Design, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, People's Republic of China.
Sauvage Center for Molecular Sciences, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, People's Republic of China.
J Phys Chem Lett. 2024 Aug 22;15(33):8410-8419. doi: 10.1021/acs.jpclett.4c01917. Epub 2024 Aug 8.
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, , 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. exhibits global aromaticity, good planarity, and suitable highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels. The protonation of in solution successively forms a stable tropylium cation and dication. Moreover, the neutral, cationic, and dicationic states of can be transformed with remarkable reversibility during the protonation-deprotonation process, as confirmed by ultraviolet-visible absorptions, fluorescence spectra, H nuclear magnetic resonance, and theoretical calculations. Additionally, we fabricate p-type organic field-effect transistor (OFET) devices based on with hole mobility up to 0.026 cm V s, 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.
非苯型多环芳烃（PAHs）因其独特的光学和电学性质而受到了广泛关注。然而，非苯型PAHs的合成及光电应用仍然具有挑战性。在此，我们通过将芘与两个薁单元稠合，提出了一种简便合成具有扶手椅型边缘的线性非苯型PAH，即 的方法。我们系统地研究了其光学和电学性质，并将其与其异构体（包括苯型和非苯型锯齿形边缘异构体）进行了比较。 具有全局芳香性、良好的平面性以及合适的最高占据分子轨道/最低未占据分子轨道能级。 在溶液中的质子化依次形成稳定的环庚三烯阳离子和双阳离子。此外，如紫外可见吸收光谱、荧光光谱、氢核磁共振以及理论计算所证实的那样， 在质子化 - 去质子化过程中，其中性、阳离子和双阳离子状态能够以显著的可逆性进行转变。此外，我们基于 制备了空穴迁移率高达0.026 cm² V⁻¹ s⁻¹ 的p型有机场效应晶体管（OFET）器件，并进一步开发了具有良好灵敏度、可回收性和选择性的基于OFET的酸蒸汽传感器。这些发现强调了由薁与并苯骨架融合产生的具有扶手椅型边缘的线性非苯型PAHs的独特性质，展示了其在有机光电子学中的潜在应用。
