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Force-induced tautomerization in a single molecule

Nature Chemistry volume 8, pages 935–940 (2016)Cite this article

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Abstract

Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed.

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Figure 1: Porphycene molecule on Cu(110) and schematic of the measurement configuration.
Figure 2: Force spectroscopy of a single porphycene molecule.
Figure 3: Force spectroscopy of a single porphycene molecule with a Xe-terminated tip.
Figure 4: Calculated force curves and MEPs for the tip–porphycene–surface system.

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Acknowledgements

J.N.L. and T.K. thank L. Grill, M. Wolf, A. Sweetman, O. Custance and A. Tkatchenko for discussions. T.K. acknowledges the support of the Morino Foundation for Molecular Science. T.F. acknowledges the support of the Basque Deptamento de Educación and the UPV/EHU (IT-756-13), the Spanish Ministerio de Economía y Competitividad (MAT2013-46593-C6-2-P) and the EU Integrated Project PAMS (610446). M.P. acknowledges computer time allocated on ARCHER through the Materials Chemistry Consortium funded by EPSRC grant no. EP/L000202, on Polaris through N8 HPC funded by EPSRC grant no. EP/K000225/1 and on Chadwick at the University of Liverpool. S.G. and J.W. acknowledge support from the Polish National Science Centre (grant no. DEC-2011/02/A/ST5/00043).

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Authors and Affiliations

  1. Department of Physical Chemistry, Fritz-Haber Institute of the Max-Planck Society, Faradayweg 4-6, Berlin, 14195, Germany

    Janina N. Ladenthin & Takashi Kumagai

  2. Donostia International Physics Center (DIPC) – UPV/EHU, San Sebastián, E-20018, Spain

    Thomas Frederiksen

  3. IKERBASQUE, Basque Foundation for Science, Bilbao, E-48013, Spain

    Thomas Frederiksen

  4. Surface Science Research Centre and Department of Chemistry, University of Liverpool, Liverpool, L69 3BX, UK

    Mats Persson & John C. Sharp

  5. Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, Warsaw, 01-224, Poland

    Sylwester Gawinkowski & Jacek Waluk

  6. Faculty of Mathematics and Natural Sciences, College of Science, Cardinal Stefan Wyszyński University, Dewajtis 5, Warsaw, 01-815, Poland

    Jacek Waluk

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  1. Janina N. Ladenthin
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Contributions

T.K. conceived the experiments. J.N.L. and T.K. performed the measurements and analysed data. T.F., M.P. and J.C.S. performed all the DFT calculations. S.G. and J.W. provided porphycene molecules. T.K. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Takashi Kumagai.

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Ladenthin, J., Frederiksen, T., Persson, M. et al. Force-induced tautomerization in a single molecule. Nature Chem 8, 935–940 (2016). https://doi.org/10.1038/nchem.2552

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