Oxygen formation through water oxidation catalysis is a key reaction in the context of fuel generation from renewable energies. The number of homogeneous catalysts that catalyze water oxidation at high rate with low overpotential is limited. Ruthenium complexes can be particularly active, especially if they facilitate a dinuclear pathway for oxygen bond formation step. A supramolecular encapsulation strategy is reported that involves preorganization of dilute solutions (10−5  m) of ruthenium complexes to yield high local catalyst concentrations (up to 0.54 m). The preorganization strategy enhances the water oxidation rate by two‐orders of magnitude to 125 s−1, as it facilitates the diffusion‐controlled rate‐limiting dinuclear coupling step. Moreover, it modulates reaction rates, enabling comprehensive elucidation of electrocatalytic reaction mechanisms.

Supramolecular self-assemblies are used across various fields for different applications including their use as containers for catalysts, drugs and fluorophores. M12L24 spheres are among the most studied, as they offer...

The hexameric undecyl-resorcin[4]­arene capsule ( C11 R 6 ) features eight discrete structural water molecules located at the vertices of its cubic suprastructure. Combining NMR spectroscopy with classical molecular dynamics (MD), we identified and characterized two distinct species of this capsule, C11 R 6 -A and C11 R 6 -B, respectively featuring 8 and 15 water molecules incorporated into their respective hydrogen-bonded networks. Furthermore, we found that the ratio of the C11 R 6 -A and C11 R 6 -B found in solution can be modulated by controlling the water content of the sample. The importance of this supramolecular modulation in C11 R 6 capsules is highlighted by its ability to perform acid-catalyzed transformations, which is an emergent property arising from the hydrogen bonding within the suprastructure. We show that the conversion of C11 R 6 -A to C11 R 6 -B enhances the catalytic rate of a model Diels–Alder cyclization by 10-fold, demonstrating the cofactor-derived control of a supramolecular catalytic process that emulates natural enzymatic systems.

The preparation of functionalized, heteroleptic PdxL2x coordination cages is desirable for catalytic and optoelectronic applications. Current rational design of these cages uses the angle between metal-binding (∠B) sites of the...