A Double-Walled Tetrahedron with Ag I 4 Vertices Binds Different Guests in Distinct Sites**
A Double-Walled Tetrahedron with Ag I 4 Vertices Binds Different Guests in Distinct Sites**
复制标题
具有 Ag I 4 个顶点的双壁四面体将不同的客人绑定在不同的地点**
DOI：
10.1002/ange.202301612
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发表时间：
2023
影响因子：
--
通讯作者：
Clark S
中科院分区：
文献类型：
--
作者：
Clark S
一种由银(I)、2-甲酰基-1，8-萘啶、卤化物和三对称三胺在溶液中组装的双壁四面体金属有机笼子。在其顶点的AgI4X簇每个都聚集了六个萘啶-亚胺基团，导致了一个结构，其中八个三位配体以(AgI4X)4L8的排列连接了四个簇。四个配体形成了一组内部的四面体壁，这些四面体的壁被外部的四个配体包围。笼子有很大的内部体积，并被观察到可以结合阴离子客人。该结构还具有外部绑定缝隙，位于笼子的边缘，用于绑定小芳香客人。观察到与银团簇结合的卤化物离子以明确的层次进行交换，从而允许对腔体积进行调制。这里揭示的原理可能允许使用越来越复杂的具有银簇顶点结构的笼子，组装后对内腔体积进行调整，从而实现有针对性的结合行为。
A double‐walled tetrahedral metal‐organic cage assembled in solution from silver(I), 2‐formyl‐1,8‐naphthyridine, halide, and a threefold‐symmetric triamine. The AgI4X clusters at its vertices each bring together six naphthyridine‐imine moieties, leading to a structure in which eight tritopic ligands bridge four clusters in an (AgI4X)4L8arrangement. Four ligands form an inner set of tetrahedron walls that are surrounded by the outer four. The cage has significant interior volume, and was observed to bind anionic guests. The structure also possesses external binding clefts, located at the edges of the cage, which bound small aromatic guests. Halide ions bound to the silver clusters were observed to exchange in a well‐defined hierarchy, allowing modulation of the cavity volume. The principles uncovered here may allow for increasingly more sophisticated cages with silver‐cluster vertex architectures, with post‐assembly tuning of the interior cavity volume enabling targeted binding behavior.