Great effort has been dedicated to the engineering of porous organic cages (POCs) in geometry and topology. Yet, harnessing these cage-like entities as premade building units to construct infinite cage-based superstructures remains elusive. In this study, we design a type of vertex-modified phosphine organic prism by a postfunctionalized approach and use it as a ditopic cage monomer to achieve an intercage supramolecular polymerization via the synergy of metal coordination and π–π dimerization. The resulting cage-by-cage polymers can further hierarchically organize into superstructures of diverse morphologies and dimensionalities, including 1D fibers, 2D lamellae, and 3D vesicles. Control over the cosolvents is capable of well regulating their structural hierarchies and self-assembled shapes. This would pave a way for the creation of cage-based supramolecular assemblies and nanomaterials.

中文翻译：

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后官能化膦有机棱柱的笼间聚合成具有可调谐形态的笼基组件


人们在多孔有机笼（POC）的几何和拓扑工程方面付出了巨大的努力。然而，利用这些笼状实体作为预制建筑单元来建造无限的基于笼子的上层建筑仍然难以实现。在本研究中，我们通过后官能化的方法设计了一种顶点修饰的膦有机棱柱，并将其用作双位笼单体，通过金属配位和π-π二聚的协同作用实现了笼间超分子聚合。由此产生的逐笼聚合物可以进一步分层组织成不同形态和维度的超结构，包括 1D 纤维、2D 片层和 3D 囊泡。对共溶剂的控制能够很好地调节它们的结构层次和自组装形状。这将为创建基于笼的超分子组件和纳米材料铺平道路。