Supramolecular blueprint approach to metal-coordinated capsules

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Abstract
An important problem in designing any large network is the assembly of systems that are resilient to change. From a chemical point of view, an analogy can be used where one requires supramolecular assemblies to maintain their dimensionality combined with limited structural perturbation in response to variation in its intermolecular framework. The identification of hydrogen-bonded framework patterns within experimentally known supramolecular assemblies that are structurally robust to disruption and selective hydrogen substitution are envisioned to act as a supramolecular blueprint or template for metal-ion retroinsertion. Here, we report the formation of a large neutral discrete pseudo-spherical coordination capsule assembled from 6 pyrogallol[4]arene ligands and 24 Cu(II) metal ions. Amazingly, this coordination capsule is structurally analogous to its hydrogen-bonded counterpart. This result shows a robust ability of pyrogallol[4]arene molecules to self-assemble into large hexameric cage structures from either the hydrogen-bonding or metal-ligand coordination process. The identification of robust supramolecular assemblies that conserve their structure in response to interchangeability between hydrogen-bonded networks for metal coordination, or inversely, represents an important advancement in supramolecular design.