Enantiopure Dual-Helical Covalent Organic Framework Nanotubes Mediated by Supramolecular Assembly

Despite significant advancements in designing covalent organic frameworks (COFs), the directed engineering of them with mesoscopic chirality remains challenging due to the dynamic equilibrium between crystallization kinetics and intermolecular interactions. Herein, we propose a biomimetic chiral supramolecular assembly-mediated (CSAM) strategy for the ambient synthesis of DNA-like bifilar helical covalent organic frameworks (H–COFs) with single-handed chirality. Simultaneously, we revealed the synergistic coupling of directional hydrogen bonding networks and steric confinement effects that governs the chiral supramolecular self-assembly process by integrating spectroscopic characterizations with computational modeling approaches. In this, the modulated supramolecular architectures mediate cooperative functionality between structural templating and catalytic activation during H–COF crystallization, effectively overcoming the inherent limitations of traditional acid-catalyzed and solvothermal approaches. Furthermore, the intrinsic functional groups and dual-helical architecture of H–COF_BTCA-TAPBcollaboratively facilitate iodine molecule adsorption and stabilization. Notably, the unique π-π stacking mode of the helical skeleton forms donor–acceptor electron transfer channels with iodine molecules. Consequently, the H–COF_BTCA-TAPB/I₂achieves a high specific capacity of 176 mAh g^–1at a current density of 0.2 A g^–1and maintains a capacity retention rate of 63% after 10,000 cycles at a high current density of 2.5 A g^–1. This work not only advances the fundamental understanding of chiral supramolecular assembly but also provides scalable ways for developing H–COFs with tailored properties.