Supramolecular Tessellations via Pillar[<i>n</i>]arenes-Based Exo–Wall Interactions

Abstract

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[<i>n</i>]arenes and prepare fantastic hexagonal supramolecular tessellations based on perethylated pillar[6]arenes (<b>EtP6</b>) with electron-deficient molecules 1,5-difluoro-2,4-dinitrobenzene (<b>DFN</b>) and tetrafluoro-1,4-benzoquinone (<b>TFB</b>). The crystal structures clearly confirm that <b>EtP6</b> can form highly ordered hexagonal 2D tiling patterns with <b>DFN</b>/<b>TFB</b> as linkers through cocrystallization. Moreover, the self-assembled packing arrangements in the ultimate cocrystal superstructures can be adjusted under different crystallization conditions. This work not only explores the rare exo-wall interactions based on pillar[<i>n</i>]arenes but also reports the fabrication of supramolecular tessellations based on pillararenes for the first time, showing a new perspective in supramolecular chemistry.