Highly Strained Electron‐Rich Molecular Bowl and Nanographene

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.