Programmed guest confinement via hierarchical cage to cage transformations.

Taking inspiration from Nature, where (bio)molecular geometry variations are exploited to tune a large variety of functions, supramolecular chemistry has continuously developed novel systems in which, as a consequence of a specific stimulus, structural changes occur. Among the different architectures, supramolecular cages have been continuously investigated for their capability to act as functional hosts where guests can be released in a controlled fashion. In this paper, a novel methodology based on the use of phenanthrenequinone is applied to selectively change the binding properties of a tris(2-pyridylmethyl)amine TPMA-based cage. In particular, subcomponent substitution has been used to change structural cage features thus controlling the inclusion ratio of competing guests differing in size or chirality.