Redox-Controlled Self-Assembly of Vanadium-Seamed Hexameric Pyrogallol[4]Arene Nanocapsules

Here we report the controlled self-assembly of vanadium-seamed metal–organic nanocapsules with specific metal oxidation state distributions. Three supramolecular assemblies composed of the same numbers of components including 24 metal centers and six pyrogallol[4]arene ligands were constructed: a V III 24 L 6 capsule, a mixed-valence V III 18 V IV 6 L 6 capsule, and a V IV 24 L 6 capsule. Crystallographic studies of the new capsules reveal their remarkable structural complexity and geometries, while marked differences in metal oxidation state distribution greatly affect the photoelectric conversion properties of these assemblies. This work therefore represents a significant step forward in the construction of intricate metal–organic architectures with tailored structure and functionality.