Perylene with Split‐Azulene Embedding
Laiyun Zhou, Fei Qiu, Yeda Ding, Jianwei Liang, Bingdi Zhou, Zheng Zhou, Lei Zhang, Chunyan Chi, Qing Wang
Abstract
Abstract Splitting the five and seven‐membered rings of azulene and embedding them separately into a conjugated backbone provides azulene‐like polycyclic aromatic hydrocarbons (PAHs), which are of great interest in quantum and material chemistry. However, the synthetic accessibility poses a significant challenge. In this study, we present the synthesis of a novel azulene‐like PAH, Pery‐57 , which can be viewed as the integration of a perylene framework into the split azulene. The compact structure of Pery‐57 displays several intriguing characteristics, including NIR II absorption at 1200 nm, a substantial dipole moment of 3.5 D, and head‐to‐tail alternating columnar packing. Furthermore, Pery‐57 exhibits remarkable redox properties. The cationic radical Pery‐57 ⋅ + readily captures a hydrogen atom. Variable‐temperature NMR (VT NMR ) and variable‐temperature EPR (VT‐EPR) studies reveal that the dianion Pery‐57 2− possesses an open‐shell singlet ground state and demonstrates significant global anti‐aromaticity. The dication Pery‐57 2+ is also predicted to exhibit diradical character. Despite bearing three bulky substituents, Pery‐57 displays p ‐type transport characteristics with a mobility of 0.03 cm 2 V −1 s −1 , attributed to its unique azulene‐like structure. Overall, this work directs interest in azulene‐like PAHs, a unique member of nonalternant PAHs showcasing exceptional properties and applications.