Construction of a Three-dimensional Covalent Organic Framework via the Linker Exchange Strategy

C ovalent organic framework(COF) is a porous crystalline material with a well-controlled structure and a wide range of potential applications. However, the construction of new COF faces huge challenges, including the design and synthesis of structural unit monomers, the choice of reaction solvent system, and the study of reaction time and temperature. So, it’s particularly important to widen the application scope of synthetic methods and further promote the development of COFs. Here, we performed structural transformations in a three-dimensional(3D) COF(COF-300), and Fourier transform infrared spectroscopy(FTIR), power X-ray diffraction analysis(PXRD) and nitrogen adsorption isotherms confirmed the chemical principles and the successful realization of these exchanges. At the same time, we found that the interpenetrating structure in 3D COF can be changed through the conversion of linkers. The structure simulation successfully proved the transformation of COF from five-fold to seven-fold interpenetration. In addition, in order to prove the versatility of this strategy, we used the same method to convert COF-300 into a high crystallinity 3D COF(TJNU-COF-302) that is also seven-fold interpenetrating and has not been reported. This simple strategy not only makes it easy to obtain a 3D COF connected with imines, which greatly promotes the development of COF, but also provides a new way to develop 3D COFs with complex interpenetrating structures.