Linear and branched supramolecular polymers formed from isomeric monomers as revealed by solution viscoelasticity

Abstract

Supramolecular polymers (SPs) assembled through non-covalent interactions provide a promising platform for designing soft materials with dynamic and tunable properties. However, the viscoelastic properties of their solutions remain poorly understood, largely due to the tendency of SP chains to bundle into thick supramolecular fibers, often resulting in precipitation or gelation. In this study, we show that bundle formation can be effectively suppressed by appropriate design of the surface of SPs through alteration of their side chains. Structural analyses revealed that the resulting SPs are homogeneously solvated, permitting their rheological characterization. Notably, we found that even subtle modifications, such as positional isomerism of the side chains, can dramatically alter the physical properties of SP solutions. Our findings, therefore, highlight the critical role of side chains in governing hierarchical structures and macroscopic properties of SPs, offering a design strategy for engineering functional supramolecular materials.