Supramolecular tessellations by the exo-wall interactions of pagoda[4]arene

Abstract

Supramolecular tessellation has gained increasing interest in supramolecular chemistry for its structural aesthetics and potential applications in optics, magnetics and catalysis. In this work, a new kind of supramolecular tessellations (STs) have been fabricated by the exo-wall interactions of pagoda[4]arene (P4). ST with rhombic tiling pattern was first constructed by P4 itself through favorable π···π interactions between anthracene units of adjacent P4. Notably, various highly ordered STs with different tiling patterns have been fabricated based on exo-wall charge transfer interactions between electron-rich P4 and electron-deficient guests including 1,4-dinitrobenzene, terephthalonitrile and tetrafluoroterephthalonitrile. Interestingly, solvent modulation and guest selection played a crucial role in controlling the molecular arrangements in the co-crystal superstructures. This work not only proves that P4 is an excellent macrocyclic building block for the fabrication of various STs, but also provides a new perspective and opportunity for the design and construction of supramolecular two-dimensional organic materials.

“Rim‐Differentiated” Pillar[6]arenes

“…In the solid state these RD‐P[6] structures can be highly adaptive, either taking 1,3,5‐alternate conformations without any open aperture or changing to rim‐differentiated ones for guest inclusion. In contrast to host–guest complexation, it is also possible to grow donor‐acceptor pillar[6]arene‐C 60 co‐crystals through exo‐wall charge transfer interactions [24c, 61] . This crystal engineering approach allows for the exploration of more technological applications of pillar[6]arene‐fullerene adducts, especially organic molecular electronics.…”

Macrocycle‐Based Crystalline Supramolecular Assemblies Built with Intermolecular Charge‐Transfer Interactions

“…Tessellation is a process to fabricate repeating patterns by arranging regular polygons to entirely cover a plane without any gaps or overlaps which not only exhibits visual and structural esthetics, but also presents wide applications in mathematics, physics, architecture, and art. Besides, the design and creation of tessellations or highly ordered superstructures at the molecular scale has also gained increasing attention and has been studied during the past decade by virtue of their potential value in magnetics, optics, and catalysis [29–33] …”

“…Besides, the design and creation of tessellations or highly ordered superstructures at the molecular scale has also gained increasing attention and has been studied during the past decade by virtue of their potential value in magnetics, optics, and catalysis. [29][30][31][32][33] The pursuit of macrocycle-based CT supramolecular tessellations can be traced back to 2014. Stoddart et al first introduced an innovative design strategy, referred to as lock-arm supramolecular ordering (LASO), aiming to construct organic CT cocrystals by a modular approach (Figure 6).…”

Biphen[n]arenes: Modular Synthesis, Customizable Cavity Sizes, and Diverse Skeletons

“…Self-assembly is another iconic feature of macrocycles and is appealing for the construction of advanced architectures and supramolecular structures. Manipulating assembling elements in a precise way is dependent on the understanding and modulation of noncovalent interactions. − The modular synthesis endows biphen­[ n ]­arenes with customizable functional units and assembly driving forces. We have constructed macrocycle-based gels driven by π···π interactions and a stimuli-responsive supramolecular assembly driven by hydrogen bonds.…”