Pd(II)‐based low‐symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such cages utilize either more than one type of symmetrical ligands (e.g., Laa, Lbb, etc.) or only one type of unsymmetrical ligand (e.g., Lab). To significantly enhance the anisotropy, we have designed two unsymmetrical bidentate ligands i.e., Lab and Lcd, aiming a low‐symmetry Pd2Lab2Lcd2‐type cage. It was accomplished by high‐fidelity integrative self‐sorting of two different low‐symmetry cages having Pd2Lab4 and Pd4Lcd8‐type architectures (homoleptic complexes of the designed ligands). Structural constraints and geometry complementarity in the ligand design drive the non‐statistical exclusive self‐assembly of the Pd2Lab2Lcd2‐type cage. By taking advantage of the complemental geometries between ligands, a low‐symmetry Pd2Lab2Lcc2‐type cage was also obtained. Heteromeric completive self‐sorting of three homoleptic assemblies (Pd2Lab4, Pd4Lcc8 and Pd4Lcd8‐type cages) into an exclusive mixture of Pd2Lab2Lcd2 and Pd2Lab2Lcc2‐type mixed ligated assemblies was demonstrated through cage‐to‐cage transformations.

中文翻译：

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异质完全自排序的高度各向异性 Pd2Lab2Lcc2 和 Pd2Lab2Lcd2 型笼


具有各向异性空腔的 Pd(II) 基低对称配位笼引起了人们的极大兴趣。实现此类笼的常用策略利用一种以上类型的对称配体（例如，Laa、Lbb等）或仅使用一种类型的不对称配体（例如，Lab）。为了显着增强各向异性，我们设计了两种不对称的二齿配体，即 Lab 和 Lcd，旨在形成低对称性的 Pd2Lab2Lcd2 型笼。它是通过具有 Pd2Lab4 和 Pd4Lcd8 型结构（设计配体的均配复合物）的两个不同的低对称性笼的高保真集成自排序来完成的。配体设计中的结构约束和几何互补性驱动了 Pd2Lab2Lcd2 型笼的非统计排他性自组装。通过利用配体之间的互补几何形状，还获得了低对称性 Pd2Lab2Lcc2 型笼。通过笼到笼的转化，证明了三个同配组装体（Pd2Lab4、Pd4Lcc8和Pd4Lcd8型笼）的异聚完全自分选为Pd2Lab2Lcd2和Pd2Lab2Lcc2型混合连接组装体的专有混合物。