A snapshot review of the crystallization of polymer chains complexed by small molecules focusing on poly(4-vinylpyridine) systems: Opportunities and challenges

Complexation of polymers using amphiphiles widens its structural diversity and chemical functionality. These complexes can exhibit crystallization when coordinated to mesogenic amphiphiles to form self-assembled supramolecular structures by allowing for rapid self-assembly and hierarchical structures. However, their behavior differs from mesogens due to intricacies involving supramolecular bonding and restricted polymer conformation. Thus, incorporating crystallizing small molecules may open avenues for low symmetry metastable structures. This snapshot overview is an attempt to review the previous work on crystallizing polymer–amphiphile systems and their behavior focusing on poly(4-vinylpiridine) systems. We discuss the effect of composition on the crystallization behavior, followed by the types of noncovalent bonding involved in these amphiphilic supramolecules. The advantages and limitations of each bonding type are discussed. The significance of advanced characterization techniques for understanding polymer complexes is highlighted by discussing the limitations and challenges in conventional methods.