Li Yu-Lin, Alexandrov Eugeny V, Yin Qi, Li Lan, Fang Zhi-Bin, Yuan Wenbing, Proserpio Davide M, Liu Tian-Fu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
Samara Center for Theoretical Material Science (SCTMS), Samara State Technical University, Molodogvardeyskaya St. 244, Samara 443100, Russia.
J Am Chem Soc. 2020 Apr 15;142(15):7218-7224. doi: 10.1021/jacs.0c02406. Epub 2020 Apr 3.
Hydrogen-bonded organic frameworks (HOFs) show great potential in many applications, but few structure-property correlations have been explored in this field. In this work, we report that self-assembly of a rigid and planar ligand gives rise to flat hexagonal honeycomb motifs which are extended into undulated two-dimensional (2D) layers and finally generate three polycatenated HOFs with record complexity. This kind of undulation is absent in the 2D layers built from a very similar but nonplanar ligand, indicating that a slight torsion of ligand produces overwhelming structural change. This change delivers materials with unique stepwise adsorption behaviors under a certain pressure originating from the movement between mutually interwoven hexagonal networks. Meanwhile, high chemical stability, phase transformation, and preferential adsorption of aromatic compounds were observed in these HOFs. The results presented in this work would help us to understand the self-assembly behaviors of HOFs and shed light on the rational design of HOF materials for practical applications.
氢键有机框架（HOFs）在许多应用中显示出巨大潜力，但该领域中很少有人探索结构与性质之间的关系。在这项工作中，我们报告了一种刚性平面配体的自组装产生了扁平的六边形蜂窝图案，这些图案延伸成起伏的二维（2D）层，最终生成了具有创纪录复杂性的三种多连锁HOFs。在由非常相似但非平面的配体构建的二维层中不存在这种起伏，这表明配体的轻微扭转会产生压倒性的结构变化。这种变化使材料在一定压力下具有独特的逐步吸附行为，这源于相互交织的六边形网络之间的移动。同时，在这些HOFs中观察到了高化学稳定性、相变以及对芳香族化合物的优先吸附。这项工作中呈现的结果将有助于我们理解HOFs的自组装行为，并为实际应用中HOF材料的合理设计提供启示。
