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

Macrocyclic 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. A new class of macrocyclic arenes (prism[2]dihydrophenazines) with tunable flexibility have been fabricated by AlCl3-catalyzed Friedel-Crafts reactions between methyl-substituted derivatives of dihydrophenazine subunits and paraformaldehyde in 1,2-dichloroethane. Cocrystallization of the flexible prism[2]dihydrophenazine with the electron-deficient guest tetrafluoro-1,4-benzoquinone resulted in regular parallelogram-like supramolecular tessellation. image