Controlled Construction of Heteroleptic [Pd 2 (L A ) 2 (L B )(L C )] 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 [Pd 12 L 24 ] and [Pd 2 L 4 ] 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 [Pd 2 L 4 ] cages. Site-selective introduction of the endo-functional group was achieved through the formation of heteroleptic [Pd 2 (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.