Since their discovery in 2008, pillar[n]arenes have been a popular family of macrocyclic arene hosts due to their accessible one-step synthesis, convenient functionalization, symmetrical prism structures and perfect cavity host–guest properties. Compared with other macrocyclic hosts, the most peculiar recognition behavior of pillararenes is the strong binding affinities of pillar[5]arenes (P5As) towards neutral guests in organic media, which is unfeasible for classic crown ethers and calixarenes. The intriguing properties have found extensive applications in many fields from supramolecular chemistry to materials science. This feature article provides a detailed summary of the molecular recognition of P5As and neutral guests, where the driving forces, binding mechanisms, and binding selectivities are comprehensively discussed. Furthermore, brief highlights of research progress in the functional applications based on the neutral guest⊂P5A motifs were also discussed, including the construction of complex topological superstructures (e.g. rotaxanes, catenanes and daisy chains), supramolecular polymers, and functional materials.

Butylated pillar[5]arene (1) and N,N′-bis(n-butyl)pyromellitic diimide (2) form a 2 : 1 sandwich-type complex external to the walls of the receptor (“exo-wall” complex). The marriage of exo-wall interactions and endo-cavity inclusion provides a new strategy for the construction of supramolecular polymers from unfunctionalized neutral receptors.

Efficient complexation of sanguinarine by carboxylatopillar[6]arene. The pK_ashift, increased solubility, and enhanced antibacterial activity are described.

Catenated cages represent chemistry’s challenging synthetic targets because a three-dimensional assembly is necessary for their formation. Herein, a cyclic bis[2]catenane is constructed through the coordination-driven self-assembly of the interlocked bis-metallacage, by the 90° Pt(II) heteroligation of the endo-functionalized double-bridged tweezer bearing pyridyl moieties and the tetra-carboxylated linker. NMR spectrometry, X-ray crystallography and mass spectrometry confirm the formation of a cyclic bis[2]catenane with “∞”-shaped topology via a 14-component self-assembly. Particularly, reversibly responsive transformation between the bis[2]catenane and the bis-metallacage can be realized by guest exchange, concentration effect and solvent effect. This work represents a novel example of a cyclic cage-based [2]catenane oligomer.

The complexation and separation of industrially important cis- and trans-1,2-dichloroethene (cis- and trans-DCE) isomers using perethylated pillar[5]arene (EtP5) are described. EtP5 exhibits considerable binding capability for the trans-DCE isomer over the cis-DCE in organic solution. Furthermore, nonporous adaptive crystals (NACs) of EtP5 can efficiently separate trans-DCE from a 50 : 50 (v/v) cis/trans-isomer mixture.