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

Area of Science:

• Supramolecular Chemistry
• Crystal Engineering
• Materials Science

Background:

• Supramolecular tessellation is an emerging field with unique structural properties and potential applications.
• Pillar[n]arenes are macrocyclic compounds with tunable properties, making them suitable for constructing complex supramolecular architectures.
• Understanding intermolecular interactions is crucial for designing ordered supramolecular assemblies.

Purpose of the Study:

• To investigate the exo-wall interactions of pillar[n]arenes.
• To fabricate hexagonal supramolecular tessellations using perethylated pillar[6]arenes (EtP6) and electron-deficient molecules.
• To explore the tunability of self-assembled packing arrangements in cocrystal superstructures.

Main Methods:

• Cocrystallization of perethylated pillar[6]arenes (EtP6) with 1,5-difluoro-2,4-dinitrobenzene (DFN) and tetrafluoro-1,4-benzoquinone (TFB).
• Single-crystal X-ray diffraction analysis to confirm the formation of hexagonal 2D tiling patterns.
• Systematic variation of crystallization conditions to study self-assembled packing arrangements.

Main Results:

• Highly ordered hexagonal 2D supramolecular tessellations were successfully prepared using EtP6 as building blocks and DFN/TFB as linkers.
• Crystal structures confirmed the formation of these tessellations through exo-wall interactions.
• The self-assembled packing arrangements within the cocrystal superstructures were found to be adjustable by altering crystallization conditions.

Conclusions:

• This work reports the first successful fabrication of supramolecular tessellations based on pillararenes.
• It demonstrates the utility of pillar[n]arenes in constructing ordered 2D supramolecular architectures through exo-wall interactions.
• The findings offer a new perspective in supramolecular chemistry and materials design.