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Supramolecular chaperones play an important role in directing the assembly of multiple protein subunits and redox-active metal ions into precise, complex and functional quaternary structures. Here we report that hydroxyl tailed C -alkylpyrogallol[4]arene ligands and redox-active Mn II ions, with the assistance of proline chaperone molecules, can assemble into two-dimensional (2D) and/or three-dimensional (3D) networked nanocapsules. Dimensionality is controlled by coordination between the exterior of nanocapsule subunits, and endohedral functionalization within the 2D system is achieved via chaperone guest encapsulation. The tailoring of surface properties of nanocapsules via coordination chemistry is also shown as an effective method for the fine-tuning magnetic properties, and electrochemical and spectroscopic studies support that the nanocapsule is an effective homogeneous water-oxidation electrocatalyst, operating at pH 6.07 with an exceptionally low overpotential of 368 mV. 

Abstract We report the synthesis of a novel metal–organic capsule constructed from six pyrogallol[4]arene macrocycles, which are switched together by 16 Fe^IIIand 16 Co^IIions. This supramolecular structure is the first instance of a spheroidal heterometallic nanocage assembled through a one‐step metal–ligand coordination approach. This new assembly also demonstrates an important proof of concept through the formation of multiple heterometallic metal–metal interactions within the capsule framework. Photophysical and electrochemical studies of self‐assembled capsule films indicate their potential as semiconductors. These materials display unexpected photoelectric conversion properties, thus representing an emergent phenomenon in discrete metal–organic supramolecular assemblies.