Single Crystalline, Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks
Single Crystalline, Non-stoichiometric Cocrystals of Hydrogen-Bonded Organic Frameworks
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DOI：
10.1002/anie.202215836
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发表时间：
2022-12-02
影响因子：
16.6
通讯作者：
Hisaki, Ichiro
中科院分区：
文献类型：
--
作者：
Hashimoto, Taito;Oketani, Ryusei;Hisaki, Ichiro
由非化学计量混合的多组分分子组成的多孔框架从功能的角度引起了人们的广泛关注。然而，它们的设计制备和精确的结构表征仍然具有挑战性。在此，我们证明了四（4-羧基苯基）六氢芘和芘衍生物（CP-Hp和CP-Py，分别）的共结晶产生非化学计量混合框架通过网络通过氢键。通过单晶X射线晶体学分析确定了骨架中CP-Hp和CP-Py的组成比，表明在宽的组成比范围内形成混合骨架。此外，对单晶的显微拉曼光谱表明，组分不是均匀分布的，如理想的固溶体，而是梯度或不均匀地进行。
Porous frameworks composed of non-stoichiometrically mixed multicomponent molecules attract much attention from a functional viewpoint. However, their designed preparation and precise structural characterization remain challenging. Herein, we demonstrate that cocrystallization of tetrakis(4-carboxyphenyl)hexahydropyrene and pyrene derivatives (CP-Hp and CP-Py, respectively) yields non-stoichiometric mixed frameworks through networking via hydrogen bonding. The composition ratio of CP-Hp and CP-Py in the framework was determined by single crystalline X-ray crystallographic analysis, indicating that the mixed frameworks were formed over a wide range of composition ratios. Furthermore, microscopic Raman spectroscopy on the single crystal indicates that the components are not uniformly distributed such as ideal solid solution, but are done gradationally or inhomogeneously.