Abstract
Although the local environment of a molecule can play an important role in its chemistry, rarely has it been examined experimentally at the level of individual molecules. Here we report the precise control of intramolecular hydrogen-transfer (tautomerization) reactions in single molecules using scanning tunnelling microscopy. By placing, with atomic precision, a copper adatom close to a porphycene molecule, we found that the tautomerization rates could be tuned up and down in a controlled fashion, surprisingly also at rather large separations. Furthermore, we extended our study to molecular assemblies in which even the arrangement of the pyrrolic hydrogen atoms in the neighbouring molecule influences the tautomerization reaction in a given porphycene, with positive and negative cooperativity effects. Our results highlight the importance of controlling the environment of molecules with atomic precision and demonstrate the potential to regulate processes that occur in a single molecule.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Hunter, C. A. & Anderson, H. L. What is cooperativity? Angew. Chem. Int. Ed. 48, 7488–7499 (2009).
Dunitz, J. D. Chemical reaction paths. Phil. Trans. R. Soc. Lond. B. 272, 99–108 (1975).
Harikumar, K. R. et al. Cooperative molecular dynamics in surface reactions. Nature Chem. 1, 716–721 (2009).
Robota, H. J., Vielhaber, W., Lin, M. C., Segner, J. & Ertl, G. Dynamics of interaction of H2 and D2 with Ni(110) and Ni(111) surfaces. Surf. Sci. 155, 101–120 (1985).
Dri, C., Peters, M. V., Schwarz, J., Hecht, S. & Grill, L. Spatial periodicity in molecular switching. Nature Nanotech. 3, 649–653 (2008).
Alemani, M. et al. Adsorption and switching properties of azobenzene derivatives on different noble metal surfaces; Au(111), Cu(111) and Au(100). J. Phys. Chem. C 112, 10509–10514 (2008).
Liljeroth, P., Repp, J. & Meyer, G. Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules. Science 317, 1203–1206 (2007).
Kim, H. W. et al. Control of molecular rotors by selection of anchoring sites. Phys. Rev. Lett. 106, 146101 (2011).
Yamachika, R., Grobis, M., Wachowiak, A. & Crommie, M. F. Controlled atom doping of a single C60 molecule. Science 304, 281–284 (2004).
Gross, L. et al. Trapping and moving metal atoms with a six-leg molecule. Nature Mater. 4, 892–895 (2005).
Repp, J., Meyer, G., Paavilainen, S., Olsson, F. E. & Persson, M. Imaging bond formation between a gold atom and pentacene on an insulating surface. Science 312, 1196–1199 (2006).
Ecija, D. et al. Assembly and manipulation of rotatable cerium porphyrinato sandwich complexes on a surface. Angew. Chem. Int. Ed. 50, 3872–3877 (2011).
Soe, W-H. et al. Manipulating molecular quantum states with classical metal atom inputs: demonstration of a single molecule NOR logic gate. ACS Nano 5, 1436–1440 (2011).
Uhlmann, C., Swart, I. & Repp, J. Controlling the orbital sequence in individual Cu–phthalocyanine molecules. Nano Lett. 13, 777–780 (2013).
Heinrich, A. J., Lutz, C. P., Gupta, J. A. & Eigler, D. M. Molecule cascades. Science 298, 1381–1387 (2002).
Nacci, C., Erwin, S. C., Kanisawa, K. & Fölsch, S. Controlled switching within an organic molecule deliberately pinned to a semiconductor surface. ACS Nano 6, 4190–4195 (2012).
Tokumaru, K., Arai, T. & Moriyama, M. Photochromism by the way of intramolecular hydrogen transfer in –N–H:N– bond. Mol. Cryst. Liq. Cryst. 246, 147–149 (1994).
Tapia, O., Andres, J. & Safont, V. S. Theoretical study of transition structures for intramolecular hydrogen transfer in molecular models representing D-ribulose 1,5-bisphosphate. A possible molecular mechanism for the enolization step in rubisco. J. Phys. Chem. 98, 4821–4830 (1994).
Joachim, C., Gimzewski, J. K. & Aviram, A. Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).
Aviram, A. & Ratner, M. Molecular rectifiers. Chem. Phys. Lett. 29, 277–283 (1974).
Heath, J. R. & Ratner, M. A. Molecular electronics. Phys. Today 56, May, 43–49 (2003).
Benesch, C. et al. Switching the conductance of a single molecule by photoinduced hydrogen transfer. J. Phys. Chem. C 113, 10315–10318 (2009).
Vogel, E., Köcher, M., Schmickler, H. & Lex, J. Porphycene – a novel porphin isomer. Angew. Chem. Int. Ed. Engl. 25, 257–259 (1986).
Sperl, A., Kröger, J. & Berndt, R. Controlled metalation of a single adsorbed phthalocyanine. Angew. Chem. Int. Ed. 50, 5294–5297 (2011).
Auwärter, W. et al. A surface-anchored molecular four-level conductance switch based on single proton transfer. Nature Nanotech. 7, 41–46 (2012).
Kozlowski, P. M., Zgierski, M. Z. & Baker, J. The inner-hydrogen migration and ground-state structure of porphycene. J. Chem. Phys. 109, 5905–5913 (1998).
Wu, Y-D. et al. Porphyrin isomers: geometry, tautomerism, geometrical isomerism, and stability. J. Org. Chem. 62, 9240–9250 (1997).
Kumagai, T. et al. Thermally and vibrationally induced tautomerization of single porphycene molecules on a Cu(110) surface. Phys. Rev. Lett. (in the press).
Gil, M. et al. Unusual, solvent viscosity-controlled tautomerism and photophysics: meso-alkylated porphycenes. J. Am. Chem. Soc. 132, 13472–13485 (2010).
Stroscio, J. A. & Celotta, R. J. Controlling the dynamics of a single atom in lateral atom manipulation. Science 306, 242–247 (2004).
Bogicevic, A. et al. Nature, strength, and consequences of indirect adsorbate interactions on metals. Phys. Rev. Lett. 85, 1910–1913 (2000).
Ram, R. S., Bernath, P. F. & Brault, J. W. Fourier transform emission spectroscopy: the vibration–rotation spectrum of CuH. J. Mol. Spectrosc. 113, 269–274 (1985).
Castro, M., Cruz, J., López-Sandoval, H. & Barba-Behrens, N. On the CH···Cu agostic interaction: chiral copper(II) compounds with ephedrine and pseudoephedrine derivatives. Chem. Commun. 3779–3781 (2005).
Haq, S. et al. Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers. J. Am. Chem. Soc. 133, 12031–12039 (2011).
Maksymovych, P., Sorescu, D. C. & Yates, J. T. Gold-adatom-mediated bonding in self-assembled short-chain alkanethiolate species on the Au(III) surface. Phys. Rev. Lett. 97, 146103 (2006).
Acknowledgements
We thank R. Ernstorfer for careful reading of the manuscript, the Japan Society for the Promotion of Science (T.K.), the German Science Foundation (SFB 658), the European Union (AtMol and ARTIST), the Polish National Science Centre (3550/B/H03/2011/40) and VR (M.P.) for financial support and EPSRC (EP/F067496) through MCC, SNIC and PRACE for computer resources at HECTOR and PDC Center for High Performance Computing.
Author information
Authors and Affiliations
Contributions
T.K. and L.G. conceived the experiments and discussed the results. T.K. performed the STM measurements and analysed the data. F.H., J.S., K.K. and M.P. carried out the DFT calculations. S.G. and J.W. provided the molecules. T.K., M.P. and L.G. wrote the paper.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 925 kb)
Rights and permissions
About this article
Cite this article
Kumagai, T., Hanke, F., Gawinkowski, S. et al. Controlling intramolecular hydrogen transfer in a porphycene molecule with single atoms or molecules located nearby. Nature Chem 6, 41–46 (2014). https://doi.org/10.1038/nchem.1804
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nchem.1804
This article is cited by
-
Voltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system
Nature Communications (2023)
-
Internal Stark effect of single-molecule fluorescence
Nature Communications (2022)
-
From molecular to supramolecular electronics
Nature Reviews Materials (2021)
-
Electron dynamics of tip-tunable oxygen species on TiO2 surface
Communications Materials (2021)
-
Single hydrogen atom manipulation for reversible deprotonation of water on a rutile TiO2 (110) surface
Communications Chemistry (2021)