The search for supramolecular reactors that contain no catalytically active sites but can promote chemical transformations has received significant attention, but it remains a synthetic challenge. Here we demonstrate a strategy of incorporating bulky and electro-rich aromatic linkers into metallocages to induce cascade reactions. Two hexahedral cages with a framework formula [(Zn₈L₆)(OTf)₁₆] are assembled from six tetrakis-bidentate ligands derived from tetraphenylethylene and eight zinc(II)tris(pyridylimine) centers. The cage cavities can accommodate different molecules such as anthranilamide and aromatic aldehyde through supramolecular interactions, allowing for a cascade condensation and cyclization to produce nonplanar 2,3-dihyroquinazolinones. The reaction is highly efficient with high rate enhancements (up to k_cat/k_uncat = 38,000) and multiple turnovers compared to the bulk reaction mixture. Control experiments and molecular simulations suggest that the acceleration is attributed to inherent strength of binding affinity for reactants and the release of products to establish catalytic turnover is due to the host-guest geometry discrepancy.

中文翻译：

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六面体配位笼的设计和自组装，用于级联反应。

寻找不包含催化活性位但能促进化学转化的超分子反应器已经引起了广泛的关注，但这仍然是一个合成挑战。在这里，我们展示了一种将庞大且富电的芳香族连接基并入金属位以诱导级联反应的策略。两个具有框架式[（Zn ₈ L ₆）（OTf）_16的六面体笼由六个由四苯基乙烯衍生的四齿双齿配体和八个锌（II）三（吡啶基嘧啶）中心组装而成。笼腔可通过超分子相互作用容纳不同的分子，例如邻氨基苯甲酰胺和芳香醛，从而允许级联缩合和环化生成非平面的2,3-二氢喹唑啉酮。 与本体反应混合物相比，该反应是高效的，具有高速率提高（高达k _cat / k _uncat = 38,000）和多个周转率。对照实验和分子模拟表明，加速归因于对反应物的结合亲和力的固有强度，而释放产物以建立催化转化是由于宿主-客体的几何差异。