Transformation of Self-Assembly Modes: From Orthogonal Coassembly to Thermodynamically Stable Specific Coassembly

The self-assembly modes in multicomponent systems may proceed under kinetic or thermodynamic control, which influence the morphologies and functional properties of these materials. Understanding the self-assembly modes of multicomponent systems provides a better platform for designing adaptive and functional materials with programmable morphologies and responsive properties. We report the different self-assembly modes of enantiomeric multicomponent systems based on terephthalic bis(valine methyl ester amide) with a flexible linker, as confirmed by SCXRD, PXRD, and NMR analyses. This study shows that coassembled networks can adopt different self-assembly modes under similar conditions, initially favoring kinetic orthogonal assembly and slowly evolving into thermodynamically specific coassembly. The spontaneous transformation of one coassembled network into another without an external stimulus is rarely observed in multicomponent systems with structurally similar components. We demonstrate the application of supramolecular gels as a medium to unravel the precise transformation of self-assembly modes in a multicomponent, enantiomeric system. Our findings highlight the crucial roles of molecular design and the conformational dynamics of individual components in forming well-ordered multicomponent systems, thereby providing a better understanding of the self-assembled networks of chiral supramolecular materials.