Controlled Construction of Heteroleptic [Pd2(LA)2(LB)(LC)]4+Cages: A Facile Approach for Site‐Selective endo‐Functionalization of Supramolecular Cavities

Construction of supramolecular structures with internal functionalities is a promising approach to build enzyme-like cavities. The endo-functionalized [Pd₁₂ L₂₄ ] and [Pd₂ L₄ ] coordination cages represent the most successful systems in this regard. However, these systems mainly contain one type of endo-moiety. We herein provide a solution for the controlled endo-functionalization of [Pd₂ L₄ ] cages. Site-selective introduction of the endo-functional group was achieved through the formation of heteroleptic [Pd₂ (L^A )₂ (L^B )(L^C )] cages. Using two orthogonal steric control elements is the key for the selective formation of the hetero-assemblies. We demonstrated the construction of two hetero-cages with a single internal functional group as well as a hetero-cage with two distinct endohedral functionalities. The endo-functionalized hetero-cages bound sulfonate guests with fast-exchange dynamics. This strategy provides a new solution for the controlled endo-functionalization of supramolecular cavities.