Bottom-Up Synthesis of Covalent Organic Frameworks with Quasi-Three-Dimensional Integrated Architecture via Interlayer Cross-Linking

Developing strategies to enhance the structural robustness of covalent organic frameworks (COFs) is of great importance. Here, we rationally design and synthesize a class of cross-linked COFs (^CCOFs), in which the two-dimensional (2D) COF layers are anchored and connected by polyethylene glycol (PEG) or alkyl chains through covalent bonds. The bottom-up fabrication of these ^CCOFs is achieved by the condensation of cross-linked aldehyde monomers and tritopic amino monomers. All the synthesized ^CCOFs possess high crystallinity and porosity, and enhanced structural robustness surpassing the typical 2D COFs, which means that they cannot be exfoliated under ultrasonication and grinding due to the cross-linking effect. Furthermore, the cross-linked patterns of PEG units are uncovered by experimental results and Monte Carlo molecular dynamics simulations. It is found that all ^CCOFs are dominated by vertical cross-layer (interlayer) connections (clearly observed in high-resolution transmission electron microscopy images), allowing them to form quasi-three-dimensional (quasi-3D) structures. This work bridges the gap between 2D COFs and 3D COFs and provides an efficient way to improve the interlayered stability of COFs.