Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition

The encapsulation of different guest molecules by their different recognition domains of proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable of selectively binding different guests in their different cavities to mimic the function of proteins are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared by multicomponent coordination-driven self-assembly. Interestingly, the porphyrin-based metallacage is capable of heteroleptic encapsulation of fullerenes (C₆₀ or C₇₀) and coronene using its different cavities, allowing distinct allosteric recognition of coronene upon the addition of C₆₀ or C₇₀. Owing to the different binding affinities of the cavities, the metallacage hosts one C₆₀ molecule in the central cavity and two coronene units in the side cavities, while encapsulating two C₇₀ molecules in the side cavities and one coronene molecule in the central cavity. The rational design of multicavity assemblies that enable heteroleptic encapsulation and allosteric recognition will guide the further design of advanced supramolecular constructs with tunable recognition properties.