Hydrogen bond, protonation, and coordination-induced supramolecular chirality inversion in glutamide-based amphiphilic self-assembly

Abstract

In this study, we have synthesized two types of Y-shaped chiral amphiphiles, namely L-BG and L-PG, with a benzene or pyridine ring at the terminal position, respectively. The optimized conformations of both amphiphiles indicate the presence of intramolecular interactions. In dimethylformamide (DMF) solution at the monomeric state, both amphiphiles exhibit positive cotton effects; however, in DMF/H2O mixed solution, the cotton effects are inverted. Molecular dynamics simulations reveal that both intermolecular and intramolecular hydrogen bonds facilitate the inversion of supramolecular chirality. Additionally, protonation and coordination of L-PG assembly results in chirality inversion and transformation of emission. This study emphasizes the significance of both inter- and intramolecular hydrogen bonds in the assembly process, providing insights into stimuli-responsive chiral supramolecular materials.