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Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface

Nature Chemistry volume 5, pages 621–627 (2013)Cite this article

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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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Figure 2: Appearance of Mn–porphyrins at the solid/liquid interface.
Figure 1: Possible pathways and states of the manganese centre of Mn-porphyrins during their reaction with O2 or with the single oxygen donor PFIB.
Figure 3: Mn–porphyrin states at the solid/liquid interface under different atmospheres.
Figure 4: Reaction of Mn–porphyrins with single oxygen donor PFIB at the graphite/1-octanoic acid interface.
Figure 5: Imaging of a μ-oxo Mn–porphyrin dimer.
Figure 6: Imaging of a reactive Mn–porphyrin state.

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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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Author notes

  1. Duncan den Boer, Min Li & Sylvia Speller

    Present address: Present address: Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA (D.B.), Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China (M.L.), Institut für Physik, University of Rostock, Rostock, Germany (S.S.),

  2. Duncan den Boer and Min Li: These authors contributed equally to this work

Authors and Affiliations

  1. Radboud University Nijmegen, Institute for Molecules and Materials (IMM), Heyendaalseweg 135, Nijmegen, 6525 AJ, The Netherlands

    Duncan den Boer, Thomas Habets, Alan E. Rowan, Roeland J. M. Nolte, Sylvia Speller & Johannes A. A. W. Elemans

  2. Division of Molecular Imaging and Photonics, KU Leuven – University of Leuven, Celestijnenlaan 200-F, Leuven, 3001, Belgium

    Min Li & Steven De Feyter

  3. Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus Universitari, Bellaterra, 08193, Catalonia, Spain

    Patrizia Iavicoli & David B. Amabilino

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Contributions

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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Correspondence to David B. Amabilino, Steven De Feyter or Johannes A. A. W. Elemans.

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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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