Highly Strained Electron‐Rich Molecular Bowl and Nanographene
Wenhao Zhang, Yeda Ding, Shimin Yu, Jiaqi Lyu, Jiaxuan Yu, Jiawen Li, Xin Zhao, Lina Feng, Jianguo Wang, Zheng Zhou, Qing Wang
Abstract
Abstract Introducing two pyrrole rings at the armchair edges of perylene creates the small, electron‐rich molecular bowl 1 , which can be viewed as a nitrogen‐doped end‐cap of C 70 . Despite numerous attempts since 2008, its synthesis has been hindered by strain and synthetic challenges. In this study, we present the synthesis and property analysis of molecular bowl 1 and its dimer, the wavy‐shaped nanographene 2 . Substituents on nitrogen atoms significantly affect the bowl depth, intermolecular interactions, and supramolecular behaviors. Consequently, the butyl‐substituted molecular bowl 1 a forms unusual polar crystals with all bowls oriented similarly, suggesting potential pyroelectric or ferroelectric applications. Due to the electron‐rich nature, compounds 1 exhibit significantly strong binding affinity towards fullerene, with 1 a forming a sandwich structure with C 70 . Furthermore, neutral bowls 1 display counter‐rotating ring currents similar to corannulene, while their dications exhibit global anti‐aromaticity. The wavy‐structured nanographene 2 demonstrates two continuously reversible oxidation processes, and its dication 2 2+ shows remarkably high stability under ambient conditions. In summary, this work constructs a small, electron‐rich molecular bowl and its nanographene dimer, highlighting their exceptional properties, promising applications, and potential as foundations for future advanced nanostructure fabrication.