Hydrogen‐bond‐regulated mechanochemical synthesis of covalent organic frameworks: cocrystal precursor strategy for confined assembly

Abstract

Two‐dimensional imine covalent organic frameworks (2D imine‐COFs) are crystalline porous materials with broad application prospects. Despite the efforts into their design and synthesis, the mechanisms of their formation are still not fully understood. Herein, a one‐pot two‐step mechanochemical cocrystal precursor synthetic strategy is developed for efficient construction of 2D imine‐COFs. The mechanistic investigation demonstrated that the cocrystal precursors of 4,4',4''‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (TAPT) and p‐toluenesulphonic acid (PTSA) sufficiently regulate the crystalline structure of COF. Evidenced by characterizations and theoretical studies, a helical hydrogen‐bond network was constructed by the N‐H···O supramolecular synthons between amine and sulfate in TAPT‐PTSA, demonstrating the role of cocrystals in promoting the organized stacking of interlayer π‐π interactions, layer arrangement, and interlayer spacing, thus facilitating the orderly assembly of COFs. Moreover, the protonation degree of TAPT amines, which tuned nucleophilic directionality, enabled the sequential progression of intra‐ and interlayer imine condensation reactions, inhibiting the formation of amorphous polymers. The transformation from cocrystal precursors to COFs was achieved through comprehensive control of hydrogen bond and covalent bond sites. This work significantly advances the concept of hydrogen‐bond‐regulated COF assembly and its mechanochemical method in the design and synthesis of 2D imine‐COFs, further elucidating the mechanistic aspects of their mechanochemical synthesis.