Ortho‐Alkoxy‐benzamide Directed Formation of a Single Crystalline Hydrogen‐bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis

Abstract Boron trifluoride (BF 3 ) is a highly corrosive gas widely used in industry. Confining BF 3 in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF 3 corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (H C OF‐50) for BF 3 storage and its application in catalysis. Specifically, we introduced self‐complementary ortho ‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate H C OFs. The H C OF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF 3 uptake. As a result, H C OF‐50 shows a record‐high 14.2 mmol/g BF 3 uptake capacity. The BF 3 uptake in H C OF‐50 is reversible, leading to the slow release of BF 3 . We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF 3 ⋅ Et 2 O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF 3 uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges.