Host‐guest chemistry, a pivotal branch of supramolecular chemistry, plays an essential role in understanding and constructing complex structures through non‐covalent interactions. Organic molecular cages, characterized by their intrinsic confined cavities, can selectively bind a variety of guest molecules. Their host‐guest chemistry has been well studied in the solution phase, and several attempts have been made to encode well‐defined molecular architectures into solid‐state polymeric materials. However, only limited studies have explored their potential in the solid state, where their lack of robustness and less ordered networks significantly hinder practical applications. Herein, we report the synthesis of a single‐crystal cage framework and a systematic study of its host‐guest chemistry, spanning from the solution state to the solid state. Our studies reveal that the host‐guest interactions inherent to the cage are successfully maintained in the solid‐state polymeric material. Furthermore, the framework's robustness allows for the guest molecules (fullerene) to be released triggered by an organic acid (trifluoracetic acid), with subsequent regeneration of the framework through an organic base (triethylamine) treatment. Our findings represent the first synthesis of a robust, single‐crystal cage framework exhibiting highly selective and reversible host‐guest chemistry, thus showing great potential towards molecular separation application.

中文翻译：

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富勒烯结合中具有高选择性和可逆性的单晶笼框架


主客体化学是超分子化学的一个关键分支，在通过非共价相互作用理解和构建复杂结构方面发挥着重要作用。有机分子笼以其固有的密闭空腔为特征，可以选择性地结合多种客体分子。它们的主客体化学在溶液相中得到了很好的研究，并且已经进行了多次尝试将明确的分子结构编码到固态聚合物材料中。然而，只有有限的研究探索了它们在固态中的潜力，它们缺乏鲁棒性和有序网络严重阻碍了实际应用。在此，我们报告了单晶笼框架的合成及其从溶液态到固态的主客体化学的系统研究。我们的研究表明，笼子固有的主客体相互作用在固态聚合物材料中得以成功维持。此外，框架的稳健性允许客体分子（富勒烯）由有机酸（三氟乙酸）触发释放，随后通过有机碱（三乙胺）处理使框架再生。我们的研究结果首次合成了一种坚固的单晶笼框架，具有高度选择性和可逆的主客体化学性质，从而显示出分子分离应用的巨大潜力。