TY - JOUR
T1 - Hierarchical organization of perylene bisimides and polyoxometalates for photo-assisted water oxidation
AU - Bonchio, Marcella
AU - Syrgiannis, Zois
AU - Burian, Max
AU - Marino, Nadia
AU - Pizzolato, Erica
AU - Dirian, Konstantin
AU - Rigodanza, Francesco
AU - Volpato, Giulia Alice
AU - La Ganga, Giuseppina
AU - Demitri, Nicola
AU - Berardi, Serena
AU - Amenitsch, Heinz
AU - Guldi, Dirk M
AU - Caramori, Stefano
AU - Bignozzi, Carlo Alberto
AU - Sartorel, Andrea
AU - Prato, Maurizio
PY - 2019
Y1 - 2019
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85058061301&partnerID=8YFLogxK
U2 - 10.1038/s41557-018-0172-y
DO - 10.1038/s41557-018-0172-y
M3 - Article
C2 - 30510216
SN - 1755-4349
VL - 11
SP - 146
EP - 153
JO - Nature Chemistry
JF - Nature Chemistry
IS - 2
ER -