Synthesis of micrometre-thick oriented 2D covalent organic framework films by a kinetic polymerization pathway
Luca Cusin, Piotr Cieciórski, Samuel Van Gele, Fabian Heck, Simon Krause, Paweł W. Majewski, Bettina V. Lotsch, Wojciech Danowski, Paolo Samorı́
Abstract
Abstract Despite advances in the field of 2D polymerization, the synthesis of high-quality, micrometre-thick films of oriented 2D covalent organic frameworks (COFs) remains challenging. Conventional approaches focusing on thermodynamic control of the polymerization pathway face a detrimental trade-off between orientation and thickness. Here we describe a straightforward method for preparing imine-linked 2D COF films with a near-perfect face-on orientation by leveraging kinetically trapped amorphous 3D covalent adaptable network (CAN) intermediates. These off-pathway intermediates are generated as coatings through solution casting, during which the CANs spontaneously align to relax tensile stresses induced by solvent evaporation. A subsequent lift-off process, followed by an amorphous-to-crystalline transformation under solvothermal conditions, converts the 3D-oriented polymer networks into thermodynamically stable, porous and free-standing 2D COF films. This versatile kinetic trapping strategy is suitable for a range of building blocks and network topologies, constituting a convenient synthetic tool for accessing high-quality, robust, large-area 2D COF films with a strongly aligned polycrystalline structure.