Highly Crystalline and Flexible Covalent Organic Frameworks: Advancing Efficient Iodine Adsorption

Abstract Flexible covalent organic frameworks (COFs) offer distinct advantages in elasticity and adaptability over rigid COFs, but these benefits often come at the expense of crystallinity due to challenges in polymerization, complicating both synthesis and structural characterization. Current research primarily employs single flexible monomers, which limits the tunability of these frameworks. In this study, we introduce two highly crystalline, flexible COFs, ZCST‐102 and ZCST‐103, constructed from dual flexible monomers. These COFs exhibit large channels, permanent porosity, high chemical stability, and exceptional crystallinity, along with enhanced structural flexibility. Notably, they achieve an iodine vapor adsorption capacity of up to 4.71 g ⋅ g −1 . X‐ray photoelectron spectroscopy, Raman spectroscopy, and electron paramagnetic resonance spectroscopy further elucidate the interactions between iodine and the framework structures. This work emphasizes the value of incorporating flexible building blocks to maintain crystallinity while imparting functional versatility, advancing the design of dynamic porous materials.