Nonlinear Supramolecular Polymers: From Controlled Synthesis, Tunable Self-Assembly Toward Diverse Applications

Nonlinear supramolecular polymers (NLSPs) exhibit the merits of reversibility and tunability, along with a unique topological structure. These features contribute to the creation of novel supramolecular polymer species and drive advancements in macromolecular engineering, making NLSPs a promising direction for generating highly functional and complex structures with diverse applications. This article reviews recent advances in NLSPs, including star, brush, hyperbranched, dendritic, cross-linked, and cyclic topological supramolecular polymers, from three key perspectives: controlled synthesis, tunable self-assembly, and functional applications. Firstly, the direct and indirect synthesis strategies used to construct various NLSPs are discussed. Subsequently, the regulation methods of supramolecular self-assembly based on NLSPs are rationalized by considering internal structure parameters and external environmental responses. Finally, comprehensive summaries of the potential applications of NLSPs in biomedical materials, photoelectric materials, self-healing materials, degradable and recycling materials, as well as catalytic materials, are provided. These applications highlight the versatility and promise of NLSPs across various industries. This article addresses key scientific problems and existing challenges in this field. With the rapidly growing area of NLSPs, it is anticipated that they will shape the future of supramolecular chemistry and polymer science, and hold great promise for research fields such as chemical engineering, biomedicine, and the environment.