Dynamic Two-Dimensional Covalent Organic Frameworks with Large Solvent-Induced Lattice Expansion

Dynamic covalent organic frameworks (COFs) can switch reversibly between crystalline phases with different unit cell parameters and porosities upon physisorption of guest molecules. While impressive changes in unit cell volumes have been realized for three-dimensional frameworks, the solvent-induced volume changes of two-dimensional (2D) COFs have remained comparably small. We have now developed a series of 2D COFs where we systematically varied the length of the interconnecting bridge units. The optimized materials achieve solvent-induced expansions of up to 85% relative to the volume of the solvent-free contracted COFs. These structural changes are fully reversible and the frameworks fully retain their high degree of crystalline order. This study introduces a versatile design strategy for dynamic 2D COFs, which could enable future applications of these materials in gas separation and sensing.