A novel low‐symmetry organic molecular cage with distinctive geometry was successfully synthesized from 5,5′‐(propane‐2,2‐diyl)bis(2‐hydroxyisophthalaldehyde) and 1,2‐cyclohexanediamine building blocks, through the desymmetrized vertex design strategy. Single‐crystal X‐ray crystallographic analysis shows that the cage contains asymmetrical and nonplanar windows, exhibiting an unprecedented C₂ symmetry and an efficient packing. The molecular cage structure was also characterized by FTIR, NMR, and MALDI‐TOF. Quantum chemistry studies show that the cage structure contains rare intramolecular hydrogen‐hydrogen (C−H⋅⋅⋅H−C) bonding interactions. The cage crystals exhibit high iodine vapor uptake (3.78 g g⁻¹), which is among the highest for porous molecular materials. The knowledge gained in this study would open new possibilities for the design and synthesis of molecular cages with novel topologies targeting a broad range of applications.

中文翻译：

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对具有异常拓扑结构的分子笼进行非对称顶点设计。

通过非对称顶点设计策略，成功地由5,5'-（丙烷-2,2-二基）双（2-羟基间苯二甲醛）和1,2-环己烷二胺结构单元合成了具有独特几何形状的新型低对称有机分子笼。X射线单晶晶体学分析表明，该笼子包含不对称和非平面的窗口，表现出前所未有的C ₂对称性和有效的填充。分子笼结构还通过FTIR，NMR和MALDI-TOF表征。量子化学研究表明，笼状结构包含罕见的分子内氢-氢键（CH-H⋅⋅⋅HC）。笼状晶体显示出高的碘蒸气吸收量（3.78 g g ^-1），是多孔分子材料中最高的。在这项研究中获得的知识将为分子笼的设计和合成开辟新的可能性，分子笼具有针对广泛应用的新颖拓扑。