Supramolecular Tessellations via Pillar[n]arenes-Based Exo-Wall Interactions

Supramolecular tessellation is a newly emerging and promising area in supramolecular chemistry because of its unique structural aesthetics and potential applications. Herein, we investigate the exo-wall interactions of pillar[n]arenes and prepare fantastic hexagonal supramolecular tessellations based on perethylated pillar[6]arenes (EtP6) with electron-deficient mole- cules 1,5-difluoro-2,4-dinitrobenzene (DFN) and tetrafluoro-1,4- benzoquinone (TFB). The crystal structures clearly confirm that EtP6 can form highly ordered hexagonal 2D tiling patterns with DFN/TFB as linkers through cocrystallization. Moreover, the self-assembled packing arrangements in the ultimate cocrystal super-structures can be adjusted under different crystallization conditions. This work not only explores the rare exo-wall interactions based on pillar[n]arenes but also reports the fabrication of supramolecular tessellations based on pillararenes for the first time, showing a new perspective in supramolecular chemistry.