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 Py₆Mes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling Py₆Mes 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 Py₆Mes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of Py₆Mes-analogues, m-Py₆Mes and Ph₆Mes.

密集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。在这里，我们报告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族分子 Py ₆ Mes 的同构多孔多晶型物。晶体结构的计算分析揭示了色散相互作用作为将 Py ₆ Mes 组装成柱状堆叠的驱动力的主要贡献，而柱在空间上是突出的并在它们之间形成纳米孔。由于疏溶剂效应，特别是在具有弱分散相互作用的溶剂中，有利于多孔填充。相反，具有强分散相互作用的溶剂由于亲溶剂效应而插入Py ₆ Mes之间并提供无孔包合物晶体。 Py ₆ Mes 类似物、 m -Py ₆ Mes 和 Ph ₆ Mes 的多晶型进一步证实了疏溶剂性导向的多晶型。