Highly Anisotropic Pd<sub>2</sub>L<sup><i>ab</i></sup><sub>2</sub>L<sup><i>cc</i></sup><sub>2</sub> and Pd<sub>2</sub>L<sup><i>ab</i></sup><sub>2</sub>L<sup><i>cd</i></sup><sub>2</sub> Type Cages by Heteromeric Completive Self‐Sorting
Minaz Parbin, Vellaiyadevan Sivalingam, Dillip Kumar Chand
Abstract
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., L aa , L bb etc.) or only one type of unsymmetrical ligand (e.g., L ab ). To significantly enhance the anisotropy, we have designed two unsymmetrical bidentate ligands i.e., L ab and L cd , aiming at a low‐symmetry Pd 2 L ab 2 L cd 2 ‐type cage. It was accomplished by high‐fidelity integrative self‐sorting of two different low‐symmetry cages having Pd 2 L ab 4 and Pd 4 L cd 8 ‐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 Pd 2 L ab 2 L cd 2 ‐type cage. By taking advantage of the complemental geometries between ligands, a low‐symmetry Pd 2 L ab 2 L cc 2 ‐type cage was also obtained. Heteromeric completive self‐sorting of three homoleptic assemblies (Pd 2 L ab 4 , Pd 4 L cc 8 and Pd 4 L cd 8 ‐type cages) into an exclusive mixture of Pd 2 L ab 2 L cd 2 and Pd 2 L ab 2 L cc 2 ‐type mixed ligated assemblies was demonstrated through cage‐to‐cage transformations.