Co-assembly of Covalent Organic Framework Particles into Binary Ordered Superstructures

Colloidal particles can co-assemble into multicomponent ordered superstructures, with their properties determined by the individual building blocks. Here, we demonstrate that covalent organic framework (COF) particles can co-assemble into binary ordered superstructures through solvent evaporation within confined spaces. By adjusting the particle size ratio, we prepare 2D COF-COF binary ordered superstructures with different stoichiometries (LS₂ and LS₆), underscoring entropic control over the assembly process. We further report the first example of co-assembly between COF and metal-organic framework (MOF) particles, presenting a 2D COF-MOF binary ordered superstructure with LS₂ stoichiometry. These results expand the design space for hybrid porous materials by enabling the construction of complex binary superstructures from COF particles of diverse sizes, shapes, porosities, and chemical compositions.