A cross-linked supramolecular polymer network gel is designed and prepared, which shows reversible gel-sol transitions induced by changes in pH, temperature, cation concentration, and metal co-ordination. The gel pore size is controlled by the amount of cross-linker added to the system, and the material can be molded into shape-persistent, free-standing objects with elastic behavior. These features are all due to the dynamically reversible host-guest complexation and good mechanical properties of the cross-linked polymer network. No single organogel has previously been reported to possess all of these features, making this supramolecular gel an unprecedentedly intelligent soft material.

Automatic repair: a polymer with pendent dibenzo[24]crown-8 units (purple in picture) was cross-linked by two bisammonium salts (green) to form two supramolecular gels based on host-guest interactions. These two gels are stimuli-responsive materials that respond to changes of the pH value and are also self-healing materials, as can be seen by eye and as evidenced by rheological data.

Copillararene convoy: A linear supramolecular polymer can be efficiently constructed in solution with a copillararene monomer (see picture). Single‐crystal X‐ray analysis and NMR spectroscopy revealed that aggregation was enthalpically driven by quadruple CH⋅⋅⋅π interactions between the octyl tail (blue) and the aromatic cavity (red).

The trans form of an azobenzene-containing guest can complex with a pillar[6]arene, while it cannot complex with pillar[5]arenes due to the different cavity sizes of the pillar[6]arene and the pillar[5]arenes. The spontaneous aggregation of its host-guest complex with the pillar[6]arene can be reversibly photocontrolled by irradiation with UV and visible light, leading to a switch between irregular aggregates and vesicle-like aggregates. This new pillar[6]arene-based photoresponsive host-guest recognition motif can work in organic solvents and is a good supplement to the existing widely used cyclodextrin/azobenzene recognition motif.

An amphiphilic pillar[5]arene was made. It could self-assemble to form vesicles and multiwalled microtubes in water. Dynamic light scattering, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, and UV-vis and FTIR spectroscopy were employed to characterize its self-assembly process and the resultant assemblies. The vesicles could encapsulate calcein within their interiors under neutral conditions and release it in response to a decrease in pH. The microtubes, which have primary amine groups on their surfaces, could adsorb TNT through donor-acceptor interactions.