Inducing chirality in covalent organic frameworks from achiral monomers: hierarchical architectures and emergent functions

Chiral covalent organic frameworks (COFs) are of significant interest for enantioselective applications. However, their synthesis has long been constrained by the difficulty of reconciling the steric bulk and low symmetry of chiral building blocks with the reversible bond formation and error correction required for crystallization. Chiral induction, which employs non-covalent or dynamic covalent interactions to bias achiral building blocks into homochiral COFs, offers a promising solution. Here we present a unified framework that organizes chiral architectures by their stereogenic origin—conformational chirality, which comprises propeller chirality (twisted C 3 -symmetric nodes) and linker conformational chirality (non-racemic dihedral angles), together with configurational (point) chirality (covalent stereocenters)—and by the length scale of their expression, from the molecular and framework level to macroscopic helical superstructures formed by hierarchical assembly. We systematically examine how different inducers and strategies selectively generate these motifs and, crucially, how each architecture dictates function. The resulting chiral frameworks have enabled a wide range of applications, including enantioselective chromatography and membrane separation, chiral fluorescence and electrochemical sensing, asymmetric catalysis, circularly polarized luminescence, and chirality-induced spin selectivity. We conclude by identifying critical gaps in structural proof, mechanistic understanding, and scalability, and outline a roadmap toward rational design and device integration.