Publisher Correction: Hierarchical organization of perylene bisimides and polyoxometalates for photo-assisted water oxidation.

In the version of this Article originally published, in the graphical abstract the y-axis units of the plot read 'mA cm-2', but should have read 'µA cm-2'. Additionally, an erroneous gap appeared in the red trace. These errors have now been corrected.

Hierarchical organization of perylene bisimides and polyoxometalates for photo-assisted water oxidation.

The oxygen in Earth's atmosphere is there primarily because of water oxidation performed by photosynthetic organisms using solar light and one specialized protein complex, photosystem II (PSII). High-resolution imaging of the PSII 'core' complex shows the ideal co-localization of multi-chromophore light-harvesting antennas with the functional reaction centre. Man-made systems are still far from replicating the complexity of PSII, as the majority of PSII mimetics have been limited to photocatalytic dyads based on a 1:1 ratio of a light absorber, generally a Ru-polypyridine complex, with a water oxidation catalyst. Here we report the self-assembly of multi-perylene-bisimide chromophores (PBI) shaped to function by interaction with a polyoxometalate water-oxidation catalyst (Ru4POM). The resulting [PBI]5Ru4POM complex shows a robust amphiphilic structure and dynamic aggregation into large two-dimensional paracrystalline domains, a redshifted light-harvesting efficiency of >40% and favourable exciton accumulation, with a peak quantum efficiency using 'green' photons (λ > 500 nm). The modularity of the building blocks and the simplicity of the non-covalent chemistry offer opportunities for innovation in artificial photosynthesis.

A Co(II)-Ru(II) dyad relevant to light-driven water oxidation catalysis.

Artificial photosynthesis aims at efficient water splitting into hydrogen and oxygen, by exploiting solar light. As a priority requirement, this process entails the integration of suitable multi-electron catalysts with light absorbing units, where charge separation is generated in order to drive the catalytic routines. The final goal could be the transposition of such an asset into a photoelectrocatalytic cell, where the two half-reactions, proton reduction to hydrogen and water oxidation to oxygen, take place at two appropriately engineered photoelectrodes. We herein report a covalent approach to anchor a Co(II) water oxidation catalyst to a Ru(II) polypyridine photosensitizer unit; photophysical characterisation and the catalytic activity of such a dyad in a light activated cycle are reported, and implications for the development of regenerative systems are discussed.

Light driven water oxidation by a single site cobalt salophen catalyst.

A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis.