Assembly of Six Types of Heteroleptic Pd₂L₄ Cages under Kinetic Control

Heteroleptic assemblies composed of several kinds of building blocks have been seen in nature. It is still unclear how natural systems design and create such complicated assemblies selectively. Past efforts on multicomponent self-assembly of artificial metal-organic cages have mainly focused on finding a suitable combination of building blocks to lead to a single multicomponent self-assembly as the thermodynamically most stable product. Here, we present another approach to selectively produce multicomponent Pd(II)-based self-assemblies under kinetic control based on the selective ligand exchanges of weak Pd-L coordination bonds retaining the original orientation of the metal centers in a kinetically stabilized cyclic structure and on local reversibility given in certain areas of the energy landscape in the presence of the assist molecule that facilitates error correction of coordination bonds. The kinetic approach enabled us to build all six types of Pd₂L₄ cages and heteroleptic tetranuclear cages composed of three kinds of ditopic ligands. Although the cage complexes thus obtained are metastable, they are stable for 1 month or more at room temperature.