Journal Article

Progress in Precision Synthesis of Supramolecular Copolymers

Satheesan, Sudheeshma, Kalathil, Krishnan Kartha, Gopalakrishnan, Anjali K., Prabhu, Deepak D.

2025

Overview

Supramolecular copolymerization has emerged as a promising tool to organize multiple components in solution. Theoretically, mixing more than one component in solution can lead to different architectures, such as narcissistic, social, blocky, and random. However, controlling the formation of a specific copolymer structure during supramolecular copolymerization remains elusive, owing to the dynamic and reversible nature of non‐covalent interactions between the constituent monomers, which facilitate rapid monomer exchange and reorganization in solution. Recent breakthroughs in the synthesis of supramolecular polymers have provided detailed mechanistic insights into supramolecular polymerization, enabling precise control over the size and morphology of the resulting assemblies. Leveraging these mechanistic insights, several attempts have been made to control supramolecular copolymerization. Rational molecular design strategies have been employed to achieve the exclusive synthesis of social and narcissistic copolymers. Conversely, tuning the subtle interplay between homo‐ and hetero‐recognition of structurally matched monomers enabled the selective formation of block copolymers. In this review, we provide an overview of rational design principles and synthetic strategies enabling the precision synthesis of supramolecular copolymers. Supramolecular copolymerization is a promising strategy for developing functional organic materials with emergent properties and applications, which are inaccessible from single‐component self‐assembly. In this proposed review, we summarize the recent advancements in the precision synthesis of supramolecular copolymers in solution.

• Subject: copolymers / donor–acceptor / pathway complexity / self‐assembly / supramolecular polymers