Chiral Matching Effect in Supramolecular Glasses via Charge-Transfer Complexation Between Foldamers and Molecular Containers.

Multicomponent supramolecular interactions offer versatile strategies for the construction and property modulation of bulk materials. Herein, we report a charge-transfer (CT)-driven host-guest chiral recognition strategy to regulate the properties of supramolecular glasses. Chiral naphthalene diimide-based cages, macrocycles, and acyclic hosts are employed to selectively complex bispyrene foldamers embedded with chiral amino acid residues. Distinct topological binding modes between the covalent cages, macrocycles, or acyclic hosts and the pyrene foldamers enable the formation of supramolecular glasses via a solvent-assisted thermal vitrification process. Solution phase spectroscopic titrations combined with density functional theory calculations elucidate and validate the chiral recognition and matching between the hosts and the foldamer guests. Importantly, in the glassy state, this chiral matching effect markedly influences key macroscopic properties, including the glass transition temperature, optical transmittance, surface roughness, and Young's modulus. As the first example of exploring chiral recognition and matching effects in glassy materials, this work provides a new molecular design paradigm for the development of functional composite glasses.