Homochirality- and Heterochirality-Controlled H- and J-Aggregation with Terminal Residue-Directed Supramolecular Chirality in Azobenzene-Based Amphiphilic Dipeptide Self-Assembly Systems

The transfer of molecular chirality to supramolecular chirality in multichiral systems constitutes a fundamental challenge in supramolecular chemistry. Azobenzene-based dipeptide amphiphiles containing chiral glutamic acid and alanine/glycine residues were designed to investigate this phenomenon. These chiral derivatives underwent spontaneous self-assembly in aqueous media, displaying characteristic circular dichroism (CD) responses. The supramolecular chiroptical properties showed critical dependence on the stereochemical configuration of terminal glutamic acid residues, with homochiral dipeptides assembling into elongated fibrillar structures whereas heterochiral analogs produced disordered aggregates. Combined density functional theory (DFT) calculations and molecular dynamics (MD) simulations revealed the stereochemical control mechanism underlying chirality transfer and morphological evolution. This systematic investigation provides enhanced understanding of hierarchical chirality propagation in multichiral architectures and establishes stereochemical design principles for programmable chiral nanomaterials.