Thermoresponsive Supramolecular Assemblies from Dendronized Amphiphiles To Form Fluorescent Spheres with Tunable Chirality

摘要

Balance between self-association of structural units and self-repulsion from crowding-induced steric hindrance accounts for the supramolecular assembly of the amphiphilic entities to form ordered structures, and solvation provides a toolbox to conveniently modulate the assemblies through differential interactions to various structural units. Here we report solvation-modulated supramolecular chiral assembly in aqueous solutions of amphiphilic dendronized tetraphenyl-ethylenes (TPEs) with three-folded dendritic oligoethylene glycols (OEGs) through dipeptide Ala-Gly linkage. These dendronized amphiphiles can form supra-molecular spheres with enhanced supramolecular chirality, which is tunable and dependent on solvation. These nanosized spherical aggregates exhibit thermoresponsive behavior, and their cloud point temperatures are dependent on mixed solvent of water and THF. The phase transition temperatures increase with water fractions due to water-driven shifting of OEG moieties from interiors of the aggregates to their peripheries. Furthermore, the thermally induced dehydration and collapse of OEG moieties mediate the reversible aggregation and deaggregation between the spheres, imparting tunable aggregation-induced fluorescent emission (AIE) and supramolecular chirality. Both experimental results and molecular dynamic simulations have highlighted that reversible chirality transformations of the amphiphilic dendronized assemblies mediated by solvation through change solvent quality or thermally dehydration are dependent on the balance between interactions of OEG dendrons with TPE moieties and with the solvent molecules.