Optical-handedness-driven enantioselective synthesis and programmable chirality encoding of covalent organic frameworks

Covalent organic frameworks (COFs) typically require chiral precursors or catalysts to achieve asymmetry. Here, we report the enantioselective synthesis of chemically chiral COFs using circularly polarized light (CP-λ) as the sole chiral director. By exploiting the reversibility of imine condensation, a dynamic self-correction process amplifies the photonic chiral bias into long-range crystalline order without any chiral auxiliaries. Unlike conventional strategies that rely on localized chiral centers, our approach induces chirality directly within the emissive framework backbone. This structural integration results in a luminescence dissymmetry factor of 0.24, representing a substantial value for purely organic systems. Furthermore, we demonstrate spatially programmable encoding with sub-micrometer resolution, enabling the transcription of complex enantiomeric patterns into the frameworks. This methodology establishes a reagent-free platform for the manufacturing of chiral crystalline materials and advances the development of programmable photonic devices. Covalent organic frameworks (COFs) typically require chiral precursors or catalysts to achieve asymmetry. Here, the authors report the enantioselective synthesis of chemically chiral COFs using circularly polarized light as the sole chiral director.