Orientational Compatibility Modulation of Ligands in Low‐Symmetry Multi‐Cavity Discrete Coordination Cages by Neighbouring Cage Participation

Abstract Complexation of Pd(II) with a designer unsymmetrical bis‐monodentate ligand (2 : 4 ratio) yielded a specific Pd 2 L 4 type “single‐cavity discrete coordination cage” (SCDCC), from a pool of 4 isomeric structures. The observed selctivity is attributed to inherent orientational preference of the ligand strands around the metal centers. Crafting a short coordinating arm at either ends of the bis‐monodentate ligand (i.e the longer‐arm) produced a pair of unsymmetrical isomeric tris‐monodentate ligands; whereas crafting the same short‐arm at both ends of the ligand gives an unsymmetrical tetrakis‐monodentate ligand. Complexation of Pd(II) with either of the isomeric tris‐monodenate ligands (3 : 4 ratio) resulted in corresponding low‐symmetry “multi‐cavity discrete coordination cage” MCDCC having two conjoined cavities, though the inherent relative orientational preference of the longer arms is not achievable in these cages. The enforced orientation is sustained by “Neighbouring Cage Participation” (NCP). However, one‐pot combination of Pd(II), with a mixture of isomeric tris‐monodentate ligands in 3 : 2 : 2 ratio produced an integratively self‐sorted mixed‐ligated MCDCC from a pool of 31 structures. Also, mixing Pd(II) with the tetrakis‐monodentate ligand produced a MCDCC having three conjoined cavities. The inherent orientational preference of longer‐arm of the ligand strands is retained in the mixed‐ligated double‐cavity and the homo‐ligated triple cavity cages.