Mild and Subtle Synthesis of β‐Ketoenamine COFs with High Crystallinity and Controllable Solubility Guided by a Monomer Preassembly Strategy

Abstract The stability of covalent organic frameworks (COFs) is crucial for their applications in demanding environments. However, increasing the stability of COFs often comes with challenges such as higher synthesis difficulty, lower crystal quality, and reduced controllability during synthesis, making it difficult to regulate dimensions and morphology, thereby impacting the processing and shaping of stable COFs. Herein, the study presents a novel confined polymerization approach guided by hydrogen bonding preassembly to synthesize a soluble and stable COF featuring β‐ketoenamine linkage. The presence of relatively weaker hydrogen bonds accelerates the orderly arrangement of monomers, ensuring appropriate spacing, and orientations among functional groups. This facilitates efficient covalent polymerization, leading to the creation of the framework while minimizing the “self‐correction” mechanism during crystal growth, thereby enhancing the efficiency of COF synthesis. Furthermore, this method offers precise control over the size of the synthesized COF. The resulting crystalline COF can be toggled between dissolution and precipitation states, facilitating the fabrication of mixed matrix membranes (MMMs) through leveraging the solubility properties of COF. Overall, this pioneering strategy yields valuable insights for advancing weak bond assembly‐mediated confined polymerization approaches, the controlled synthesis of stable COFs, and the preparation and processing of soluble COFs in diverse applications.