The development of novel systems for the polyoxometalate–organic cage (POC) is an attractive research field for their fascinating topological structures and well-defined functional cavities. Here, we report the successful self-assembly of anionic POC architectures {XW₉Ni₆L₃}₄ (X = Si or P and L = p-aminobenzoic acid), comprising Ni₆-substituted trivacant lacunary polyoxometalate (POM) and the organic ligand with both rigid COOH and flexible coordination NH₂ groups. It is worth noting a Keggin {XW₁₂} (X = Si or P) in the interior cavity, which is not encountered in reported POCs. More remarkably, in the cage architecture, the chiral C₃ conformation was generated based on asymmetric coordination arrangement of ligands, which results in the deviation of the polyhedra and the helical arrangement of the ligands and finally constitutes the hierarchical chirality of the {POM₄L₁₂} cages. The solution stability, magnetic behavior, and dye adsorption of {SiW₁₂}@{SiW₉Ni₆L₃}₄ have also been investigated.

中文翻译：

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两个带有 Td─Keggin 模板的 Pseudo-T 多金属氧酸盐-有机笼

多金属氧酸盐-有机笼 (POC) 的新型系统的开发因其迷人的拓扑结构和明确定义的功能腔而成为一个有吸引力的研究领域。在这里，我们报告了阴离子 POC 架构的成功自组装 {XW ₉ Ni ₆ L ₃ } ₄（X = Si 或 P 和 L =对氨基苯甲酸），其中包含 Ni ₆ -取代的三空基缺位多金属氧酸盐 (POM) 和具有刚性 COOH 和柔性配位 NH ₂基团的有机配体。值得注意的是 Keggin {XW ₁₂}（X = Si 或 P）在内腔中，这在报告的 POC 中没有遇到。更值得注意的是，在笼结构中，基于配体的不对称配位排列产生了手性C 3 构象，导致多面体的偏离和配体的螺旋排列，最终构成了{POM 4 L的_分级手性₁₂ }笼子。还研究了{SiW ₁₂ }@{SiW ₉ Ni ₆ L ₃ } ₄的溶液稳定性、磁性和染料吸附。