Ortho ‐Alkoxy‐benzamide Directed Formation of a Single Crystalline Hydrogen‐bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis
Ortho ‐Alkoxy‐benzamide Directed Formation of a Single Crystalline Hydrogen‐bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis
复制标题
邻-烷氧基-苯甲酰胺定向形成单晶氢键交联有机框架及其三氟化硼的吸收和催化
DOI：
10.1002/anie.202311601
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Schmidt‐Rohr, Klaus
中科院分区：
文献类型：
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作者：
Li, Fangzhou;Li, Errui;Samanta, Krishanu;Zheng, Zhaoxi;Wu, Lianqian;Chen, Albert D.;Farha, Omar K.;Staples, Richard J.;Niu, Jia;Schmidt‐Rohr, Klaus
三氟化硼(BF3)是一种工业上广泛使用的高腐蚀性气体。将BF3限制在多孔材料中，确保安全和方便的处理，并防止其降解。因此，开发高吸附容量、高稳定性、耐BF3腐蚀的多孔材料是人们迫切需要的。本文设计合成了一种用于BF3储存的Lewis碱性单晶氢键交联有机骨架(HCOF-50)及其在催化中的应用。具体地说，我们引入了自互补的邻烷氧基苯甲酰胺氢键部分来指导形成高度组织的氢键网络，这些网络随后被光交联来生成HCOF。HCOF-50具有Lewis碱性硫醚键和富含电子的孔表面，可用于BF3的吸收。结果表明，HCOF-50表现出创纪录的14.2mmo1/g BF3吸收能力。HCOF-50对BF3的摄取是可逆的，导致BF3的缓慢释放。我们利用这一特性来减少乙烯基醚阳离子聚合中不希望发生的链转移和终止。与使用BF3、⋅ 和Et2O合成的聚合物相比，合成的聚合物具有更高的相对分子质量和更低的多分散性。单晶X射线结构提供的结构-性质关系的阐明，加上BF3的高吸收能力和受控吸附，突出了分子对框架-客体相互作用的理解，以应对当代的挑战。
Boron trifluoride (BF3) is a highly corrosive gas widely used in industry. Confining BF3in 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 BF3corrosion. Herein, we designed and synthesized a Lewis basic single‐crystalline hydrogen‐bond crosslinked organic framework (HCOF‐50) for BF3storage and its application in catalysis. Specifically, we introduced self‐complementaryortho‐alkoxy‐benzamide hydrogen‐bonding moieties to direct the formation of highly organized hydrogen‐bonded networks, which were subsequently photo‐crosslinked to generate HCOFs. The HCOF‐50 features Lewis basic thioether linkages and electron‐rich pore surfaces for BF3uptake. As a result, HCOF‐50 shows a record‐high 14.2 mmol/g BF3uptake capacity. The BF3uptake in HCOF‐50 is reversible, leading to the slow release of BF3. 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 BF3⋅ Et2O. The elucidation of the structure–property relationship, as provided by the single‐crystal X‐ray structures, combined with the high BF3uptake capacity and controlled sorption, highlights the molecular understanding of framework‐guest interactions in addressing contemporary challenges.