An overview from simple host–guest systems to progressively complex supramolecular assemblies

Supramolecular chemistry involving macrocyclic hosts is a highly interdisciplinary and fast-growing research field in chemistry, biochemistry, and materials science. Host-guest based supramolecular assemblies, as constructed through non-covalent interactions, are highly dynamic in nature, and can be tuned easily using their responses to various external stimuli, providing a convenient approach to achieve excellent functional materials. Macrocyclic hosts, particularly cyclodextrins, cucurbit[n]urils, and calix[n]arenes, which have unique features like possessing hydrophobic cavities of different sizes, along with hydrophilic external surfaces, which are also amenable towards easy derivatizations, are versatile cavitands or host molecules to encapsulate diverse guest molecules to form stable host-guest complexes with many unique structures and properties. Interestingly, host-guest complexes possessing amphiphilic properties can easily lead to the formation of various advanced supramolecular assemblies, like pseudorotaxanes, rotaxanes, polyrotaxanes, supramolecular polymers, micelles, vesicles, supramolecular nanostructures, and so on. Moreover, these supramolecular assemblies, with varied morphologies and responsiveness towards external stimuli, have immense potential for applications in nanotechnology, materials science, biosensors, drug delivery, analytical chemistry and biomedical sciences. In this perspective, we present a stimulating overview, discussing simple host-guest systems to complex supramolecular assemblies in a systematic manner, aiming to encourage future researchers in this fascinating area of supramolecular chemistry to develop advanced supramolecular materials with superior functionalities, for their deployment in diverse applied areas.