层内氢键在用于催化 Suzuki-Miyaura 交叉偶联反应的腙连接的纳米孔共价有机骨架的快速结晶中的作用,ACS Applied Nano Materials

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层内氢键在用于催化 Suzuki-Miyaura 交叉偶联反应的腙连接的纳米孔共价有机骨架的快速结晶中的作用
ACS Applied Nano Materials ( IF 5.3 ) Pub Date : 2023-01-26 , DOI: 10.1021/acsanm.2c04652
Yogendra Nailwal ₁ , Matthew A. Addicoat ₂ , Manisha Gaurav ₁ , Santanu Kumar Pal ₁

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共价有机框架 (COF) 是新兴的智能材料，可以通过针对各种应用调整其结构多样性和拓扑结构来设计和合成。尽管 COF 的设计取得了巨大进步，但构建 COF 的合成方法始终是一个重大挑战。在此，我们展示了通过合成的基于腙的Bth-Tp-COF 的快速结晶苯-1,3,5-三碳酰肼 (Bth) 和三甲酰间苯三酚 (Tp) 接头在搅拌条件下发生的席夫碱反应。COF 的生长通常在 30 分钟内完成，并且可能由 COF 层中的层内和层间氢键驱动，导致快速结晶。在这里，层内氢键阻止面内键旋转，而层间氢键为 COF 层提供刚性，有利于反平行堆叠模型。发现合成的Bth-Tp-COF在 12 M HCl、12 M NaOH、TFA 和水中等刺激性化学品中高度稳定 5 天。此外，当我们在Bth-Tp-COF中掺杂钯 (Pd) 时，得到的Pd/Bth-Tp-COF被发现是用于 Suzuki-Miyaura 交叉偶联反应的高效多相催化剂，该反应在仅 20 分钟的快速反应时间内完成，收率高。此外，Pd/Bth-Tp-COF在回收实验中表现出高活性，其结晶度在多达五个催化循环时略有下降。COF 中的快速结晶和金属掺杂策略为开发用于各种化学转化的优异多相催化剂提供了多种机会。

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Role of Intralayer Hydrogen Bonding in the Fast Crystallization of the Hydrazone-Linked Nanoporous Covalent Organic Framework for Catalytic Suzuki–Miyaura Cross-Coupling Reactions

Covalent organic frameworks (COFs) are the emerging smart materials that can be designed and synthesized by tuning their structural diversity and topology for various applications. Despite vast advancements in the design of COFs, the synthetic methodologies to construct COFs are always a significant challenge. Herein, we demonstrate a fast crystallization in hydrazone-based Bth-Tp-COF, synthesized via a Schiff-base reaction between benzene-1,3,5-tricarbohydrazide (Bth) and triformylphloroglucinol (Tp) linkers under stirred conditions. The growth of the COF was typically completed in 30 min and likely driven by intra- and interlayer hydrogen bonding in COF layers, leading to the fast crystallization. Here, the intralayer hydrogen bonding prevented in-plane bond rotation, while the interlayer hydrogen bonding provided rigidity to the COF layers favoring the antiparallel stacking model. The synthesized Bth-Tp-COF was found to be highly stable in harsh chemicals such as 12 M HCl, 12 M NaOH, TFA, and water for 5 days. Moreover, when we doped palladium (Pd) in Bth-Tp-COF, the resulting Pd/Bth-Tp-COF was found to be a highly efficient heterogeneous catalyst for the Suzuki–Miyaura cross-coupling reaction that completed in a quick reaction time of only 20 min with excellent yields. In addition, Pd/Bth-Tp-COF displayed high activity in the recycling experiment with a slight decrease in its crystallinity up to five catalytic cycles. The fast crystallization and metal doping strategy in COFs open up several opportunities to develop excellent heterogeneous catalysts for various chemical transformations.

更新日期：2023-01-26

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