Abstract：
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.
摘要：
具有各向异性腔的基于Pd（II）的低对称性配位笼引起了极大的兴趣。用于实现此类笼子的常见策略利用了一种以上类型的对称配体（例如，Laa,Lbb,等。)或仅一种类型的不对称配体(例如，实验室）。为了显著增强各向异性，我们设计了两个不对称的双齿配体，即，实验室和Lcd，瞄准低对称性Pd2Lab2Lcd2型保持架。这是通过具有Pd2Lab4和Pd4Lcd8型结构（所设计配体的同质配合物）的两个不同的低对称笼的高保真集成自分选来实现的。配体设计中的结构约束和几何互补性驱动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。通过笼到笼的转换，证明了将三个同型装配体（Pd2Lab4，Pd4Lcc8和Pd4Lcd8型笼）异聚完成自分类为Pd2Lab2Lcd2和Pd2Lab2Lcc2型混合结扎装配体的独家混合物。
