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A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II

Nature Chemistry volume 8, pages 576–583 (2016)Cite this article

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Abstract

Mimicking the ingenuity of nature and exploiting the billions of years over which natural selection has developed numerous effective biochemical conversions is one of the most successful strategies in a chemist's toolbox. However, an inability to replicate the elegance and efficiency of the oxygen-evolving complex of photosystem II (OEC-PSII) in its oxidation of water into O2 is a significant bottleneck in the development of a closed-loop sustainable energy cycle. Here, we present an artificial metallosupramolecular macrocycle that gathers three Ru(bda) centres (bda = 2,2′-bipyridine-6,6′-dicarboxylic acid) that catalyses water oxidation. The macrocyclic architecture accelerates the rate of water oxidation via a water nucleophilic attack mechanism, similar to the mechanism exhibited by OEC-PSII, and reaches remarkable catalytic turnover frequencies >100 s–1. Photo-driven water oxidation yields outstanding activity, even in the nM concentration regime, with a turnover number of >1,255 and turnover frequency of >13.1 s–1.

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Figure 1: Synthesis and characterization of macrocycle [Ru(bda)bpb]3.
Figure 2: Electrochemical and spectroelectrochemical investigation of [Ru(bda)bpb]3.
Figure 3: Catalytic performance of macrocycle [Ru(bda)bpb]3.
Figure 4: Kinetic isotope experiments for [Ru(bda)pic2] and [Ru(bda)bpb]3.
Figure 5: Potential mechanistic pathways for water oxidation catalysis and proposed hydrogen-bonding network in macrocycle [Ru(bda)bpb]3.
Figure 6: Photocatalytic water oxidation experiment using [Ru(bda)bpb]3 as catalyst.

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Acknowledgements

This work was supported by the Bavarian Research Program ‘Solar Technologies Go Hybrid’. M.S. thanks the Fonds der Chemischen Industrie for a Kekulé fellowship. The authors thank M. Büchner (MS facility, Universität Würzburg) for help with the 18O labelling experiment. The authors also thank R. Mitrić and M.I.S. Röhr (Institute for Physical and Theoretical Chemistry, Universität Würzburg) for the DFT calculations.

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Authors and Affiliations

  1. Universität Würzburg, Institut für Organische Chemie and Center for Nanosystems Chemistry, Am Hubland, Würzburg, 97074, Germany

    Marcus Schulze, Valentin Kunz, Peter D. Frischmann & Frank Würthner

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  1. Marcus Schulze
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  2. Valentin Kunz
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  3. Peter D. Frischmann
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Contributions

P.D.F. and F.W. conceived the concept of metallosupramolecular macrocyclic water oxidation catalysts. M.S. and V.K. established the experimental methodologies and performed the reported experiments. M.S. wrote the manuscript with support from all co-authors.

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Correspondence to Frank Würthner.

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Schulze, M., Kunz, V., Frischmann, P. et al. A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II. Nature Chem 8, 576–583 (2016). https://doi.org/10.1038/nchem.2503

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