Prism[2]dihydrophenazines: Synthesis, Configurational Analysis, and Supramolecular Tessellation through Exo‐Wall Interactions

Abstract

AbstractMacrocyclic arenes have gained considerable attention for their structural diversity and widespread applications. In this research, a new kind of macrocyclic arenes, namely prism[2]dihydrophenazines (anti‐P2P20, syn‐P2P20, and P2P22), composed of two dihydrophenazine derivatives subunits bridged by methylene groups, were conveniently synthesized by AlCl3‐catalyzed one‐pot condensation in 1,2‐dichloroethane. Both anti‐P2P20 and its isomer syn‐P2P20 exhibited flexible and convertible conformation with narrow cavity, while P2P22 possessed rigid and rhombic‐like skeleton due to the more steric hindrance on subunits. In addition, the selection of electron‐deficient guest was found to influence the outside binding behavior of syn‐P2P20. Fantastic regular supramolecular tessellation was fabricated by tiling of syn‐P2P20 with tetrafluoro‐1,4‐benzoquinone (TFB) through the exo‐wall interactions. Using 1,5‐difluoro‐2,4‐dinitrobenzene (DFN) as a linker, only the regular 2D network superstructure with periodic units in a plane was obtained through cocrystallization. This work not only reports the construction of supramolecular tessellations by using prism[2]dihydrophenazines as building blocks, but also provides a new perspective for the design of macrocyclic arenes and fabrication of 2D supramolecular materials.