Yamagishi Hiroshi, Tsunoda Monika, Iwai Kohei, Hengphasatporn Kowit, Shigeta Yasuteru, Sato Hiroyasu, Yamamoto Yohei
Department of Materials Science, Faculty of Pure and Applied Sciences, and Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba, Tsukuba, Ibaraki, Japan.
Center for Computational Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan.
Commun Chem. 2021 Aug 20;4(1):122. doi: 10.1038/s42004-021-00561-8.
Dense packing is a universal tendency of organic molecules in the solid state. Typical porous crystals utilize reticular strong intermolecular bonding networks to overcome this principle. Here, we report a solvophobicity-based methodology for assembling discrete molecules into a porous form and succeed in synthesizing isostructural porous polymorphs of an amphiphilic aromatic molecule PyMes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling PyMes into a columnar stacking while the columns are sterically salient and form nanopores between them. The porous packing is facilitated particularly in solvents with weak dispersion interaction due to the solvophobic effect. Conversely, solvents with strong dispersion interaction intercalate between PyMes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of PyMes-analogues, m-PyMes and PhMes.
紧密堆积是固态有机分子的普遍趋势。典型的多孔晶体利用网状强分子间键合网络来克服这一原理。在此，我们报道了一种基于疏溶剂性的方法，用于将离散分子组装成多孔形式，并成功合成了两亲性芳香分子PyMes的同构多孔多晶型物。对晶体结构的计算分析表明，色散相互作用是将PyMes组装成柱状堆积的主要驱动力，而这些柱状结构在空间上突出，并且在它们之间形成纳米孔。由于疏溶剂效应，多孔堆积在具有弱色散相互作用的溶剂中尤为有利。相反，由于亲溶剂效应，具有强色散相互作用的溶剂会插入PyMes之间，并提供无孔包合晶体。PyMes类似物m-PyMes和PhMes的多晶型物进一步证实了疏溶剂性导向的多晶型现象。
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