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.

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The data supporting the findings of this study are available within the article and its Supplementary Information files. All other relevant source data are available from the corresponding authors upon request.

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Change history

  • 13 March 2019

    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.


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This work was supported by the Italian Ministero dell’Istruzione, Università e Ricerca (FIRB RBAP11C58Y, PRIN-2010N3T9M4), the Universities of Padova and Trieste, INSTM, and the Seventh Framework Programme (FP7/2007–2013) under grant agreement no. 310651 (SACS project). Beamtime obtained at the facilities ELETTRA- Sincrotrone Trieste S.C.p.A. and CERIC-ERIC consortium is acknowledged.

Author information


  1. CNR-ITM and Dipartimento di Scienze Chimiche, University of Padova, Padova, Italy

    • Marcella Bonchio
    • , Zois Syrgiannis
    • , Nadia Marino
    • , Erica Pizzolato
    • , Giulia Alice Volpato
    •  & Andrea Sartorel
  2. Center of Excellence for Nanostructured Materials (CENMAT) and INSTM, unit of Trieste, Department of Chemical and Pharmaceutical Sciences, University of Trieste, Trieste, Italy

    • Zois Syrgiannis
    • , Erica Pizzolato
    • , Francesco Rigodanza
    •  & Maurizio Prato
  3. Institute of Inorganic Chemistry, Graz University of Technology, Graz, Austria

    • Max Burian
    •  & Heinz Amenitsch
  4. Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials, Erlangen, Germany

    • Konstantin Dirian
    •  & Dirk M. Guldi
  5. Dipartimento di Scienze Chimiche, Università di Messina and Centro Interuniversitario per la Conversione Chimica dell’Energia Solare, Messina, Italy

    • Giuseppina La Ganga
  6. Elettra-Sincrotrone Trieste, Trieste, Italy

    • Nicola Demitri
  7. Department of Chemistry and Pharmaceutical Sciences and CNR-ISOF, University of Ferrara, Ferrara, Italy

    • Serena Berardi
    • , Stefano Caramori
    •  & Carlo Alberto Bignozzi
  8. CIC BiomaGUNE, San Sebastián, Spain

    • Maurizio Prato
  9. Basque Foundation for Science, Ikerbasque, Bilbao, Spain

    • Maurizio Prato


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Z.S., E.P. and F.R. carried out the synthesis and characterization experiments. M.Burian and H.A. conducted the WAXS and SAXS structural investigations. N.M. isolated and characterized the hexagonal crystalline aggregates. N.M. and N.D. conducted the X-ray diffraction analysis. K.D. and D.M.G. designed and analysed the fsTA studies. G.A.V. and G.L. optimized the oxygenic activity and photocurrent performance. S.B., S.C. and C.A.B. conducted the photoelectrochemical cell experiments. A.S. analysed the solution and photoelectrochemical cell results. M.Bonchio and M.P. designed the experiments and wrote the paper.

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The authors declare no competing interests.

Corresponding authors

Correspondence to Marcella Bonchio or Maurizio Prato.

Supplementary information

  1. Supplementary Information

    Supplementary Materials and Methods, Supplementary Figs 1–18, Supplementary Tables 1 and 2

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