Due to the existing challenges in the synthesis of covalently linked large organic cages, the potential benefits of such gigantic structures have been less explored, comparatively. Here, we present a one-pot, template-free strategy to construct a porphyrin-based gigantic organic cage P₁₂L₂₄, built with 12 square-shaped porphyrins (P) and 24 bent linkers (L). Single crystal X-ray analysis of P₁₂L₂₄ revealed a cuboctahedron structure with a diameter of ∼5.3 nm reminiscent of the COPII protein with a cuboctahedral geometry. To the best of our knowledge, it represents the largest, pure organic synthetic cage reported so far. By virtue of its large voids facilitating mass transport of substrates, 3a efficiently catalyzes the photooxidation of dihydroxynaphthalene derivatives in a heterogeneous setting, corroborating the benefits of these structures. Additionally, we demonstrate the insertion of a linear guest molecule into Zn-metallated cage Zn-3b in solution, which may facilitate the synthesis of multivariate gigantic cages in the future.

由于在共价连接的大型有机笼子的合成中存在挑战，因此，相对而言，这种巨大结构的潜在优势尚未得到充分研究。在这里，我们提出了一种无罐，无模板的策略，以构建一个基于卟啉的巨型有机笼P ₁₂ L ₂₄，该笼由12个方形卟啉（P）和24个弯曲接头（L）组成。对P ₁₂ L _24的单晶X射线分析显示了一个立方八面体结构，其直径约为5.3 nm，让人联想到具有立方八面体几何形状的COPII蛋白。据我们所知，它代表了迄今为止报道的最大的纯有机合成笼子。由于其较大的空隙，有利于基材的大量运输，3a在异质环境中有效催化二羟基萘衍生物的光氧化作用，从而证实了这些结构的优势。此外，我们证明了将线性客体分子插入溶液中的Zn金属化笼子Zn- 3b中，这可能会在将来促进多变量巨型笼子的合成。