Supramolecular Polymerization from Controllable Fabrication to Living Polymerization

Supramolecular polymers have attracted plenty of interest in the scientific community; however, developing controllable methods of supramolecular polymerization remains a serious challenge. This article reviews some recent developments of methods for supramolecular polymerization from controllable fabrication to living polymerization. Three facile methods with general applicability for controllable fabrication of supramolecular polymers have been established recently: the first method is a self‐sorting approach by manipulating ring–chain equilibrium based on noncovalent control over rigidity of monomers; the second is covalent polymerization from supramonomers formed by noncovalent interactions; and the third is supramolecular interfacial polymerization. More excitingly, living supramolecular polymerization has been achieved by two elegant strategies, including seeded supramolecular polymerization under pathway complexity control and chain‐growth supramolecular polymerization by metastable monomers. It is anticipated that this review may provide some guidance for precise fabrication of supramolecular polymers, leading to the construction of supramolecular polymeric materials with controllable architectures and functions. Methods of supramolecular polymerization from controllable fabrication to living polymerization have been recently developed. The self‐sorting approach, supramonomer method, and supramolecular interfacial polymerization extend methods of supramolecular polymerization for controllable fabrication under thermodynamic control. Furthermore, seeded polymerization under pathway complexity and chain‐growth polymerization advance the living supramolecular polymerization upon kinetic control. These developments are summarized in this article.