Hybrid[4]arene-Based Supramolecular Tessellations Driven by Exo-Wall Interaction

As an emerging field in supramolecular chemistry, supramolecular tessellations have attracted more and more attention because of their potential application prospects. Herein, we construct novel supramolecular tessellation systems by the exowall complexation of an electron-rich macrocycle hybrid[4]arene (H) with electron-deficient guests tetrafluoroterephthalonitrile (DCTFB), 1,2,4,5-tetracyanobenzene (TCNB), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). By analyzing their crystal structures, it is found that H can form highly ordered two-dimensional tiled planar structures with electron-deficient guests driven by charge-transfer interactions. The structure of H is deformed when complexed with various electron-deficient guests. According to their independent gradient model, we find that the reason for this phenomenon is the change in noncovalent interactions between H and these guests. This study not only opens up the potential of hybrid[n]arenes-based macrocyclic building blocks but also provides valuable insights into the construction of diverse two-dimensional organic structures.