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Mimicking the electron donor side of Photosystem II in artificial photosynthesis

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Abstract

This review focuses on our recent efforts in synthetic ruthenium–tyrosine–manganese chemistry mimicking the donor side reactions of Photosystem II. Tyrosine and tryptophan residues were linked to ruthenium photosensitizers, which resulted in model complexes for proton-coupled electron transfer from amino acids. A new mechanistic model was proposed and used to design complexes in which the mechanism could be switched between concerted and step-wise proton-coupled electron transfer. Moreover, a manganese dimer linked to a ruthenium complex could be oxidized in three successive steps, from Mn II,II2 to Mn III,IV2 by the photo-oxidized ruthenium sensitizer. This was possible thanks to a charge compensating ligand exchange in the manganese complex. Detailed studies of the ligand exchange suggested that at high water concentrations, each oxidation step is coupled to a proton-release of water-derived ligands, analogous to the oxidation steps of the manganese cluster of Photosystem II.

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Abbreviations

ETPT:

electron transfer followed by proton transfer

EXAFS:

extended X-ray absorption fine structure

PTET:

proton transfer followed by electron transfer

P680 :

the central, primary donor chlorophylls of Photosystem II

TyrZ :

the redox-active tyrosine of the D1 protein of Photosystem II

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Acknowledgements

All present and past collaboration partners and coworkers of the Swedish Consortium for Artificial Photosynthesis are gratefully acknowledged, in particular Björn Åkermark and Licheng Sun (Stockholm) for synthetic work and a long-standing collaboration. This work was financed by The Swedish Energy Agency, The Knut and Alice Wallenberg Foundation, The Swedish Research Council, The Royal Swedish Academy of Sciences, The Swedish Foundation for Strategic Research, DESS and NEST-STRP `SOLAR-H' (EU contract no 516510).

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Authors and Affiliations

  1. Department of Physical Chemistry, Uppsala University, Box 579, 751 23, Uppsala, Sweden

    Reiner Lomoth, Martin Sjödin & Leif Hammarström

  2. Department of Molecular Biomimetics, Uppsala University, Villavägen 6, 752 36, Uppsala, Sweden

    Ann Magnuson, Ping Huang & Stenbjörn Styring

  3. National Centre for Sensor Research, Dublin City University, Glasnevin, 9, Dublin, Ireland

    Martin Sjödin

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  1. Reiner Lomoth
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  2. Ann Magnuson
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  3. Martin Sjödin
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  4. Ping Huang
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  5. Stenbjörn Styring
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  6. Leif Hammarström
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Correspondence to Leif Hammarström.

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Lomoth, R., Magnuson, A., Sjödin, M. et al. Mimicking the electron donor side of Photosystem II in artificial photosynthesis. Photosynth Res 87, 25–40 (2006). https://doi.org/10.1007/s11120-005-9005-0

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