%0 Journal Article
%T Perylene with Split-Azulene Embedding.
%A Zhou L
%A Qiu F
%A Ding Y
%A Liang J
%A Zhou B
%A Zhou Z
%A Zhang L
%A Chi C
%A Wang Q
%J Angew Chem Int Ed Engl
%V 0
%N 0
%D 2024 Jul 10
%M 38982974
%F 16.823
%R 10.1002/anie.202409750
%X 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-572- possesses an open-shell singlet ground state and demonstrates significant global anti-aromaticity. The dication Pery-572+ 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 cm2 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.