Dynamic H‐Bonding Mediates Stimuli‐Responsive Chiral Induction in Porous Aromatic Cages with Multicolor Chiral Afterglow

Abstract

Abstract The origin of biological chirality remains a fundamental scientific mystery. Developing artificial systems with on‐off responsive chiral induction and transfer, and elucidating their mechanisms, is of paramount importance. Here, we report the first pair of chiral porous organic cage ( R/S ‐ BA‐PAC ) exhibiting unprecedented chiral afterglow in a film state, boosting a remarkable lifetime of 1.2 s and a dissymmetry factor ( g lum ) of 0.001. Loading rhodamine B (RB) guest molecules enables multicolor afterglow ranging from green to red, achieving 88% energy transfer. Notably, the confined RB displays a pronounced mirror‐imaged circular dichroism signal, and the induced chirality of RB demonstrates completely reversible on‐off switching under water vapor/thermal stimulation, which is extremely rare in covalent porous materials. Experimental and theoretical studies have shown that the distortion of the benzoic acid moiety in RB is caused by hydrogen‐bonding interactions between benzoic acid group and the BA‐PAC . This distortion disrupts the electric‐magnetic dipole moment orthogonality of RB, inducing its chirality. Furthermore, the reversible disruption and reconstruction of the host–guest hydrogen‐bonding network induced by external stimuli is a key mechanism for dynamic chiral transfer. This study bridges chiral induction and stimuli response in porous cages, providing a versatile biomimetic platform for investigating molecular‐level dynamic chirality transfer.