Monocyclic and Dicyclic Dehydro[20]annulenes Integrated with Perylene Diimide

A novel kind of monocyclic and dicyclic dehydro[20]annulenes exhibiting specific sizes and topologies from regioselective unilateral ortho‐diethynyl PDI, is developed by Cu‐catalyzed Glaser–Hay homo‐coupling and cross‐coupling. Through the integration of electron‐deficient PDI chromophores into the dehydroannulene scaffolding, these macrocycles exhibit intense and characteristic absorption properties and the degenerated LUMO levels. The single‐crystal X‐ray diffraction analysis unambiguously revealed unique porous supramolecular structures, which display micropore characteristics with surface area of 120.74 m 2  g −1 . A moderate electron mobility of 0.05 cm 2  V −1  s −1 for chlorine‐free dehydro[20]annulene based on micrometer‐sized single‐crystalline transistors was witnessed. The porous and yet semiconducting features signify the prospects of PDI‐integrated dehydroannulenes in organic optoelectronics.