Geometrically Mismatched Hydrogen-bonded Framework Composed of Tetratopic Carboxylic Acid
Geometrically Mismatched Hydrogen-bonded Framework Composed of Tetratopic Carboxylic Acid
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由四位羧酸组成的几何失配氢键骨架
DOI：
10.1002/chem.202201571
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Ichiro Hisaki
中科院分区：
文献类型：
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作者：
Zhuxi Yang;Taito Hashimoto;Ryusei Oketani;Takayoshi Nakamura;Ichiro Hisaki
孔中具有相互作用的自由位点的多孔有机框架因其具有显示位点来源的特定功能的潜力而备受关注。在此，我们证明可以使用由基于菲咯啉的四位羧酸CP-Phen组成的几何不匹配框架的概念来构建这样的框架。 CP-Phen的简单重结晶得到了一种包含多孔骨架的溶剂CP-Phen-1，其中四个羧基中的三个形成氢键二聚体，形成梯形骨架，而剩下的一个由于几何不匹配而不参与骨架形成，并通过弱氢键与溶剂分子相互作用。这一结果意味着我们提出的策略对于在多孔框架中提供免费的交互站点是有效的。尽管CP-Phen-1经历了两步结构转变，可能伴随着溶剂分子损失时的氢键重排，但活化的骨架在高达360°C的温度下表现出良好的热稳定性和选择性CO2吸附。
Porous organic frameworks possessing interactive free sites in the pore have attracted much attention due to their potential to show the site‐originated specific functionalities. Herein, we demonstrate that such a framework could be constructed using a concept of geometrically mismatched frameworks composed of phenanthroline‐based tetratopic carboxylic acidCP‐Phen. Simple recrystallization ofCP‐Phenyielded a solvent included porous frameworkCP‐Phen‐1, in which three of four carboxy groups form hydrogen‐bonded dimer to form a ladder‐shaped framework, while the remained one does not participate in framework formation due to geometrical mismatch and interacts with solvent molecules through weak hydrogen‐bonding. This result implies that our proposed strategy is effective to provide free interactive sites in porous frameworks. AlthoughCP‐Phen‐1undergoes two‐step structural transformation presumably accompanied by hydrogen‐bond rearrangements upon loss of solvent molecules, the activate framework shows good thermal stability up to 360 °C and selective CO2adsorption.