The construction and application of metal–organic cages with accessible internal cavities have witnessed rapid development, however, the precise synthesis of complex metal–organic capsules with multiple cavities and achievement of multi-guest encapsulation, and further in-depth comprehension of host–multi-guest recognition remain a great challenge. Just like building LEGO blocks, herein, we have constructed a series of high-order layered metal–organic architectures of generation n (n = 1/2/3/4 is also the number of cavities) by multi-component coordination-driven self-assembly using porphyrin-containing tetrapodal ligands (like plates), multiple parallel-podal ligands (like clamps) and metal ions (like nodes). Importantly, these high-order assembled structures possessed different numbers of rigid and separate cavities formed by overlapped porphyrin planes with specific gaps. The host–guest experiments and convincing characterization proved that these capsules G2–G4 could serve as host structures to achieve multi-guest recognition and unprecedentedly encapsulate up to four C₆₀ molecules. More interestingly, these capsules revealed negative cooperation behavior in the process of multi-guest recognition, which provides a new platform to further study complicated host–multi-guest interaction in the field of supramolecular chemistry.

中文翻译：

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高阶层状自组装多腔金属——有机胶囊与反主-多客体化学

具有可进入内腔的金属有机笼的构建和应用得到了快速发展，然而，具有多个空腔的复杂金属有机胶囊的精确合成和多客体封装的实现，以及对主多体的进一步深入理解- 客人的认可仍然是一个巨大的挑战。就像搭建乐高积木一样，在这里，我们通过多组件协调驱动的自组装构建了一系列n代高阶层状金属有机结构（n = 1/2/3/4也是空腔的数量） -使用含卟啉的四足配体（如板）、多个平行足配体（如夹子）和金属离子（如节点）进行组装。重要的是，这些高阶组装结构具有不同数量的刚性且独立的空腔，这些空腔由具有特定间隙的重叠卟啉平面形成。主客体实验和令人信服的表征证明，这些胶囊G2-G4可以作为主体结构实现多客体识别，并前所未有地封装多达四个 C ₆₀分子。更有趣的是，这些胶囊在多客体识别过程中揭示了负合作行为，这为进一步研究超分子化学领域复杂的主多客体相互作用提供了新的平台。