Abstract
Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.
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Acknowledgements
NanoNed (the Dutch nanotechnology initiative of the Ministry of Economic Affairs), the Foundation for Fundamental Research on Matter (FOM programme Atomic and Molecular Nanophysics) and the Ministry of Education, Culture and Science (Gravity program 024.001.035) are acknowledged for financial support. D.B.A. acknowledges funding from projects CTQ2010-16339 and 2009 SGR 158. S.D.F. acknowledges support from the Fund of Scientific Research−Flanders (FWO), KU Leuven (GOA) and the Belgian Federal Science Policy Office (IAP-P7/05). J.A.A.W.E. and T.H. thank the Council for the Chemical Sciences of The Netherlands Organisation for Scientific Research (CW-NWO) for a Vidi grant (700.58.423) and an ECHO grant (700.57.023), respectively. J.A.A.W.E. thanks the European Research Council for an ERC Starting Grant (NANOCAT – 259064).
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J.A.A.W.E., S.D.F. and D.B.A. conceived the idea and designed the experiments. D.d.B. and M.L. performed the STM experiments. T.H. and D.d.B. carried out data analyses, and P.I. synthesized and characterized the compound. D.d.B., M.L. and J.A.A.W.E. co-wrote the paper. All authors analysed and discussed the results and commented on the manuscript.
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den Boer, D., Li, M., Habets, T. et al. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface. Nature Chem 5, 621–627 (2013). https://doi.org/10.1038/nchem.1667
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DOI: https://doi.org/10.1038/nchem.1667
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