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

Bonchio, Marcella; Syrgiannis, Zois; Burian, Max; Marino, Nadia; Pizzolato, Erica; Dirian, Konstantin; Rigodanza, Francesco; Volpato, Giulia Alice; La Ganga, Giuseppina; Demitri, Nicola; Berardi, Serena; Amenitsch, Heinz; Guldi, Dirk M.; Caramori, Stefano;

NATURE CHEMISTRY
2019
VL / 11 - BP / 146 - EP / 153
abstract
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](5)Ru4POM 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 (lambda > 500 nm). The modularity of the building blocks and the simplicity of the non-covalent chemistry offer opportunities for innovation in artificial photosynthesis.

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