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Di Giovannantonio M, Tomellini M, Lipton-Duffin J, et al. Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization. J Am Chem Soc. 2016;138(51):16696-16702doi: 10.1021/jacs.6b09728.
Di Giovannantonio, M., Tomellini, M., Lipton-Duffin, J., Galeotti, G., Ebrahimi, M., Cossaro, A., Verdini, A., Kharche, N., Meunier, V., Vasseur, G., Fagot-Revurat, Y., Perepichka, D. F., Rosei, F., & Contini, G. (2016). Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization. Journal of the American Chemical Society, 138(51), 16696-16702. https://doi.org/10.1021/jacs.6b09728
Di Giovannantonio, Marco, et al. "Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization." Journal of the American Chemical Society vol. 138,51 (2016): 16696-16702. doi: https://doi.org/10.1021/jacs.6b09728
Di Giovannantonio M, Tomellini M, Lipton-Duffin J, Galeotti G, Ebrahimi M, Cossaro A, Verdini A, Kharche N, Meunier V, Vasseur G, Fagot-Revurat Y, Perepichka DF, Rosei F, Contini G. Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization. J Am Chem Soc. 2016 Dec 28;138(51):16696-16702. doi: 10.1021/jacs.6b09728. Epub 2016 Dec 13. PMID: 27958750.
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J Am Chem Soc. 2016 Dec 28;138(51):16696-16702. doi: 10.1021/jacs.6b09728. Epub 2016 Dec 13.

Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization.

Journal of the American Chemical Society

Marco Di Giovannantonio, Massimo Tomellini, Josh Lipton-Duffin, Gianluca Galeotti, Maryam Ebrahimi, Albano Cossaro, Alberto Verdini, Neerav Kharche, Vincent Meunier, Guillaume Vasseur, Yannick Fagot-Revurat, Dmitrii F Perepichka, Federico Rosei, Giorgio Contini

Affiliations

  1. Istituto di Struttura della Materia, CNR , Via Fosso del Cavaliere 100, 00133 Roma, Italy.
  2. Institute for Future Environments, Queensland University of Technology (QUT) , 2 George Street, Brisbane, Queensland 4001, Australia.
  3. Centre Énergie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique , 1650 Boulevard Lionel-Boulet, Varennes, Quebec J3X 1S2, Canada.
  4. CNR-IOM , Laboratorio TASC, 34149 Trieste, Italy.
  5. Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute , 110 Eighth Street, Troy, New York 12180, United States.
  6. Donostia International Physics Center (DIPC) , Paseo Manuel Lardizabal 4, 20018 San Sebastián, Spain.
  7. Institut Jean Lamour, UMR 7198, Université de Lorraine/CNRS , B.P. 70239, Vandoeuvre-Les-Nancy F-54506, France.
  8. Department of Chemistry, McGill University , 801 Sherbrooke Street, West Montreal, Quebec H3A 0B8, Canada.
  9. Institute for Fundamental and Frontier Science, University of Electronic Science and Technology of China , Chengdu 610054, PR China.

PMID: 27958750 DOI: 10.1021/jacs.6b09728

Abstract

Surface-confined polymerization via Ullmann coupling is a promising route to create one- and two-dimensional covalent π-conjugated structures, including the bottom-up growth of graphene nanoribbons. Understanding the mechanism of the Ullmann reaction is necessary to provide a platform for rationally controlling the formation of these materials. We use fast X-ray photoelectron spectroscopy (XPS) in kinetic measurements of epitaxial surface polymerization of 1,4-dibromobenzene on Cu(110) and devise a kinetic model based on mean field rate equations, involving a transient state. This state is observed in the energy landscapes calculated by nudged elastic band (NEB) within density functional theory (DFT), which assumes as initial and final geometries of the organometallic and polymeric structures those observed by scanning tunneling microscopy (STM). The kinetic model accounts for all the salient features observed in the experimental curves extracted from the fast-XPS measurements and enables an enhanced understanding of the polymerization process, which is found to follow a nucleation-and-growth behavior preceded by the formation of a transient state.

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