The swelling-shrinking transition of hydrogels is crucial for their wide applications such as actuators and drug delivery. We hereby fabricated a smart hydrogel with ferrocene groups on pendant of polymer networks. While it was immersed in the water-soluble pillar[6]arene (WP6) aqueous solution, the hydrogel was dramatically swollen, which was an approximately 11-fold promotion in weight compared with that in pure water, due to the formation of the inclusion complexes between WP6 and ferrocene groups in the hydrogel. In particular, the well-swollen hydrogel exhibited good responsiveness to multistimuli including temperature, pH, redox, and competitive guests by tuning the dissociation/formation of WP6-ferrocene inclusion complexes or the strength of their charges. Meanwhile, potential application of such a smart hydrogel in pH-responsive drug release was demonstrated as well.

A dual-responsive supramolecular network based on pillar[6]arene−ferrocenium redox-controllable recognition motifs in polymeric backbones is constructed with a ferrocenium-functionalized copolymer and a pillar[6]arene copolymer, in which the first example of pillar[6]arene-functionalized copolymer was synthesized through the reversible addition/ fragmentation chain-transfer copolymerization of an acrylate-functionalized pillar[6]arene and methyl acrylate. The resulting supramolecular network exhibits dramatically increased viscosity than the non-cross-linked mixtures and demonstrates a gel-like behavior on macroscale with a transient-network behavior revealed by rheology study. Furthermore, the viscoelastic properties of such supramolecular network can be easily controlled by different external stimuli including redox stimulus and competing host/ guest reagents.

Photoresponsive materials (PRMs) have long been a hot topic and photo‐modulated smart surface is very appealing. Particularly, liquid crystalline PRMs are able to amplify and stabilize photoinduced orientation thanks to their self‐assembling and ordering characteristics. Herein, the first pillararene‐based azobenzene liquid crystalline PRM with well‐defined structure is presented, which can avoid the usually ill‐defined composition drawback of polymer PRMs and prevent the severe H‐aggregation from suppressing or even completely blocking photoresponse in simple azobenzene derivatives. The pillar[5]arene‐based macrocyclic azobenzenes with variant length spacers show wide temperature range smectic liquid crystalline mesophases and excellent film‐formation property. The tubular pillar[5]arene macrocyclic framework provides sufficient free volume for azobenzene moieties to achieve reversible photoisomerization and photoalignment; thus, their thin films demonstrate excellent light‐triggered modulation of surface free energy, wettability, and even photoalignment‐mediated orientation of an upper layer discotic liquid crystal columnar mesophase. Such pillararene‐based azobenzene liquid crystals represent novel and promising PRMs with extensive fascinating applications.

Ureidopyrimidinone functionalized pillar[5]arene (UPyP5) was synthesized and employed to complex with a bisparaquat derivative (G) to form supramolecular polymers at relatively high concentration. The orthogonal binding interactions including quadruple hydrogen bonding and host-guest interaction should play vital roles in the construction of this linear assembly.

A bis-urea-functionalized pillar[5]arene has been synthesized and shown to form [2]pseudorotaxanes spontaneously with linear alkyl dicarboxylates in highly polar solvent DMSO, in which the hydrogen bonding interactions between the bis-urea hydrogens and dicarboxylate oxygens play an important role in stabilizing the novel [2]pseudorotaxanes alongside C-Hπ interactions.