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.

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).

A new family of discrete hexakis-pillar[5]arene metallacycles with different sizes have been successfully prepared via coordination-driven self-assembly, which presented very few successful examples of preparation of discrete multiple pillar[n]arene derivatives. These newly designed hexakis-pillar[5]arene metallacycles were well characterized with one-dimensional (1-D) multinuclear NMR ((1)H and (31) P NMR), two-dimensional (2-D) (1)H-(1)H COSY and NOESY, ESI-TOF-MS, elemental analysis, and PM6 semiempirical molecular orbital methods. Furthermore, the host-guest complexation of such hexakis-pillar[5]arene hosts with a series of different neutral ditopic guests G1-6 were well investigated. Through host-guest interactions of hexakis-pillar[5]arene metallacycles H2 or H3 with the neutral dinitrile guest G5, the cross-linked supramolecular polymers H2⊃(G5)3 or H3⊃(G5)3 were successfully constructed at the high-concentration region, respectively. Interestingly, these cross-linked supramolecular polymers transformed into the stable supramolecular gels upon increasing the concentrations to a relatively high level. More importantly, by taking advantage of the dynamic nature of metal-ligand bonds and host-guest interactions, the reversible multiple stimuli-responsive gel-sol phase transitions of such polymer gels were successfully realized under different stimuli, such as temperature, halide, and competitive guest, etc. The mechanism of such multiple stimuli-responsive processes was well illustrated by in situ multinuclear NMR investigation. This research not only provides a highly efficient approach to the preparation of discrete multiple pillar[n]arene derivatives but also presents a new family of multiple stimuli-responsive "smart" soft matters.

Highly selective binding of basic amino acids, i.e. lysine, arginine, and histidine, by a negatively charged carboxylatopillar[5]arene (CP5A) is reported. And the complexation behavior of the CP5A host towards lysine metabolites including cadaverine (Cad), acetyl-l-lysine (AcLys) and trimethyl-l-lysine (TMLys) is also described.

A host–guest recognition motif based on a crown ether moiety was employed to construct a supramolecular polymer gel from a low molecular weight A–B monomer. Reversible thermo‐ and pH‐induced gel–sol transitions of the dual‐responsive gel are demonstrated for the controlled release of rhodamine B.