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Steric and electronic selectivity in the synthesis of Fe-1,2,4,5-tetracyanobenzene (TCNB) complexes on Au(111): From topological confinement to bond formation

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Abstract

A study of the surface assisted self-assembly of 1,2,4,5-tetracyanobenzene (TCNB) acceptor molecules and Fe atoms on an Au(111) surface is presented. While conditions to get the two-dimensional arrays of stable Fe(TCNB)4 complexes are clearly identified, ultrahigh vacuum scanning tunneling microscopy and spectroscopy (STM/STS) coupled with first-principles calculations reveals that situations may occur where Fe and TCNB survive on the surface (as Fe-4TCNB entities) at a higher density than the original molecular monolayer without forming coordination bonds with each other. It is found that the square planar coordination of the Fe(TCNB)4 monomer complexes cannot fully develop in the presence of lateral strain due to growth-induced confinement. A phenomenon similar to steric hindrance involving a strongly modified chirality with a Fe-N-C bond angle of 120° compared to the 180° for the stable complex may then explain why the Fe atom keeps its metallic bond with the surface. The competition between steric and electronic effects, not reported before, may arise elsewhere in surface chemistry involved in the synthesis of new and potentially useful organic nanomaterials.

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References

  1. de Oteyza, D. G.; Gorman, P.; Chen, Y. -C.; Wickenburg, S.; Riss, A.; Mowbray, D. J.; Etkin, G.; Pedramrazi, Z.; Tsai, H. -Z.; Rubio, A., et al. Direct imaging of covalent bond structure in single-molecule chemical reactions. Science 2013, 340, 1434–1437.

    Article  Google Scholar 

  2. Hla, S. -W.; Bartels, L.; Meyer, G.; Rieder, K. -H. Inducing all steps of a chemical reaction with the scanning tunneling microscope tip: Towards single molecule engineering. Phys. Rev. Lett. 2000, 85, 2777–2780.

    Article  Google Scholar 

  3. 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 2006, 312, 1196–1199.

    Article  Google Scholar 

  4. Barth, J. V. Molecular architectonic on metal surfaces. Annu. Rev. Phys. Chem. 2007, 58, 375–407.

    Article  Google Scholar 

  5. Ruben, M.; Rojo, J.; Romero-Salguero, F. J.; Uppadine, L. H.; Lehn, J. -M. Grid-type metal ion architectures: Functional metallosupramolecular arrays. Angew. Chem. Int. Ed. 2004, 43, 3644–3662.

    Article  Google Scholar 

  6. Stepanow, S.; Lingenfelder, M.; Dmitriev, A.; Spillmann, H.; Delvigne, E.; Lin, N.; Deng, X. B.; Cai, C. Z.; Barth, J. V.; Kern, K. Steering molecular organization and host-guest interactions using two-dimensional nanoporous coordination systems. Nat. Mater. 2004, 3, 229–233.

    Article  Google Scholar 

  7. Messina, P.; Dmitriev, A.; Lin, N.; Spillmann, H.; Abel, M.; Barth, J. V.; Kern, K. Direct observation of chiral metal-organic complexes assembled on a Cu(100) surface. J. Am. Chem. Soc. 2002, 124, 14000–14001.

    Article  Google Scholar 

  8. Dmitriev, A.; Spillmann, H.; Ligenfelder, M.; Lin, N.; Barth, J. V.; Kern, K. Design of extended surface-supported chiral metal-organic arrays comprising mononuclear iron centers. Langmuir 2004, 20, 4799–4801.

    Article  Google Scholar 

  9. Gambardella, P.; Stepanow, S.; Dmitriev, A.; Honolka, J.; de Groot, F. M. F.; Lingenfelder, M.; Gupta, S. S.; Sarma, D. D.; Bencok, P.; Stanescu, S., et al. Supramolecular control of the magnetic anisotropy in two-dimensional high-spin Fe arrays at a metal interface. Nat. Mater. 2009, 8, 189–193.

    Article  Google Scholar 

  10. Schlickum, U.; Decker, R.; Klappenberger, F.; Zoppellaro, G.; Klyatskaya, S.; Ruben, M.; Silanes, I.; Arnau, A.; Kern, K.; Brune, H., et al. Metal-organic honeycomb nanomeshes with tunable cavity size. Nano Lett. 2007, 7, 3813–3817.

    Article  Google Scholar 

  11. Schlickum, U.; Klappenberger, F.; Decker, R.; Zoppellaro, G.; Klyatskaya, S.; Ruben, M.; Kern, K.; Brune, H.; Barth, J. V. Surface-confined metal-organic nanostructures from Co-directed assembly of linear terphenyl-dicarbonitrile linkers on Ag(111). J. Phys. Chem. C 2010, 114, 15602–15606.

    Article  Google Scholar 

  12. Abdurakhmanova, N.; Tseng, T. -C.; Langner, A.; Kley, C. S.; Sessi, V.; Stepanow, S.; Kern, K. Superexchange-mediated ferromagnetic coupling in two-dimensional Ni-TCNQ networks on metal surfaces. Phys. Rev. Lett. 2013, 110, 027202.

    Article  Google Scholar 

  13. Tseng, T. -C.; Abdurakhmanova, N.; Stepanow, S.; Kern, K. Hierarchical assembly and reticulation of two-dimensional Mn- and Ni-TCNQx (x = 1, 2, 4) coordination structures on a metal surface. J. Phys. Chem. C 2011, 115, 10211–10217.

    Article  Google Scholar 

  14. Faraggi, M. N.; Jiang, N.; Gonzalez-Lakunza, N.; Langner, A.; Stepanow, S.; Kern, K.; Arnau, A. Bonding and charge transfer in metal-organic coordination networks on Au(111) with strong acceptor molecules. J. Phys. Chem.C 2012, 116, 24558–24565.

    Article  Google Scholar 

  15. Abdurakhmanova, N.; Floris, A.; Tseng, T. -C.; Comisso, A.; Stepanow, S.; De Vita, A.; Kern, K. Stereoselectivity and electrostatics in charge-transfer Mn- and Cs-TCNQ4 networks on Ag(100). Nat. Commun. 2012, 3, 940.

    Article  Google Scholar 

  16. Yang, H. -H.; Chu, Y. -H.; Lu, C. -I.; Yang, T. -H.; Yang, K. -J.; Kaun, C. -C.; Hoffmann, G.; Lin, M. -T. Digitized charge transfer magnitude determined by metal-organic coordination number. ACS Nano, 2013, 7, 2814–2819.

    Article  Google Scholar 

  17. Wang, W. H.; Shi, X. Q.; Wang, S. Y.; Liu, J.; Van Hove, M. A.; Liu, P. N.; Zhang, R. -Q.; Lin, N. Cooperative modulation of electronic structures of aromatic molecules coupled to multiple metal contacts. Phys. Rev. Lett. 2013, 110, 046802.

    Article  Google Scholar 

  18. Wegner, D.; Yamachika, R.; Wang, Y. Y.; Brar, V. W.; Bartlett, B. M.; Long, J. R.; Crommie, M. F. Single-molecule charge transfer and bonding at an organic/inorganic interface: Tetracyanoethylene on noble metals. Nano Lett. 2008, 8, 131–135.

    Article  Google Scholar 

  19. Abel, M.; Clair, S.; Ourdjini, O.; Mossoyan, M.; Porte, L. Single layer of polymeric Fe-phthalocyanine: An organometallic sheet on metal and thin insulating film. J. Am. Chem. Soc. 2011, 133, 1203–1205.

    Article  Google Scholar 

  20. Repp, J.; Meyer, G.; Rieder, K. -H. Snell’s law for surface electrons: Refraction of an electron gas imaged in real space. Phys. Rev. Lett. 2004, 92, 036803.

    Article  Google Scholar 

  21. Temirov, R.; Soubatch, S.; Luican, A.; Tautz F. S. Free-electron-like dispersion in an organic monolayer film on a metal substrate. Nature 2006, 444, 350–353.

    Article  Google Scholar 

  22. Heinrich, B. W.; Limot, L.; Rastei, M. V.; Iacovita, C.; Bucher, J. P.; Djimbi, D. M.; Massobrio, C.; Boero, M. Dispersion and localization of electronic atates at a ferrocene/Cu(111) interface. Phys. Rev. Lett. 2011, 107, 216801.

    Article  Google Scholar 

  23. Ziroff, J.; Gold, P.; Bendounan, A.; Forster, F.; Reinert, F. Adsorption energy and geometry of physisorbed organic molecules on Au(111) probed by surface-state photoemission. Surf. Sci. 2009, 603, 354–358.

    Article  Google Scholar 

  24. Hückstädt, C.; Schmidt, S.; Hüfner, S.; Forster, F.; Reinert, F.; Springborg, M. Work function studies of rare-gas/noble metal adsorption systems using a Kelvin probe. Phys. Rev. B 2006, 73, 075409.

    Article  Google Scholar 

  25. Rangger, G. M.; Romaner, L.; Hofmann, O. T.; Heimel, G.; Ramsey, M. G.; Zojer, E. Analysis of bonding between conjugated organic molecules and noble metal surfaces using orbital overlap populations. J. Chem. Theory Comput. 2010, 6, 3481–3489.

    Article  Google Scholar 

  26. Madhavan, V.; Chen, W.; Jamneala, T.; Crommie, M. F.; Wingreen, N. S. Local spectroscopy of a Kondo impurity: Co on Au(111). Phys. Rev. B 2001 , 64, 165412.

    Article  Google Scholar 

  27. Olsson, F. E.; Persson, M.; Borisov, A. G.; Gauyacq, J. -P.; Lagoute, J.; Fölsch, S. Localization of the Cu(111) surface state by single Cu adatoms. Phys. Rev. Lett. 2004, 93, 206803.

    Article  Google Scholar 

  28. Boero, M.; Terakura, K.; Ikeshoji, T.; Liew, C. C.; Parrinello, M. Hydrogen bonding and dipole moment of water at supercritical conditions: A first-principles molecular dynamics study. Phys. Rev. Lett. 2000, 85, 3245–3248.

    Article  Google Scholar 

  29. Yu, M.; Xu, W.; Kalashnyk, N.; Benjalal, Y.; Nagarajan, S.; Masini, F.; Lægsgaard, E.; Hliwa, M.; Bouju, X.; Gourdon, A., et al. From zero to two dimensions: Supramolecular nanostructures formed from perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and Ni on the Au(111) surface through the interplay between hydrogen-bonding and electrostatic metal-organic interactions. Nano Res. 2012, 5, 903–916.

    Article  Google Scholar 

  30. Isvoranu, C.; Wang, B.; Ataman, E.; Schulte, K.; Knudsen, J.; Andersen, J. N.; Bocquet, M. -L.; Schnadt, J. Pyridine adsorption on single-layer iron phthalocyanine on Au(111). J. Phys. Chem. C 2011, 115, 20201–20208.

    Article  Google Scholar 

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Authors and Affiliations

  1. Institut de Physique et Chimie des Matériaux de Strasbourg, CNRS UMR 7504, Université de Strasbourg, F-67034, Strasbourg, France

    Shawulienu Kezilebieke, Anis Amokrane, Mauro Boero & Jean-Pierre Bucher

  2. IM2NP, CNRS UMR 7334, Université Aix-Marseille, Campus de Saint-Jérôme, Case 142, F-13397, Marseille Cedex 20, France

    Sylvain Clair & Mathieu Abel

Authors
  1. Shawulienu Kezilebieke
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  2. Anis Amokrane
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  3. Mauro Boero
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  4. Sylvain Clair
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  5. Mathieu Abel
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  6. Jean-Pierre Bucher
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Correspondence to Jean-Pierre Bucher.

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Kezilebieke, S., Amokrane, A., Boero, M. et al. Steric and electronic selectivity in the synthesis of Fe-1,2,4,5-tetracyanobenzene (TCNB) complexes on Au(111): From topological confinement to bond formation. Nano Res. 7, 888–897 (2014). https://doi.org/10.1007/s12274-014-0450-y

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  • DOI: https://doi.org/10.1007/s12274-014-0450-y

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