On-Surface Polymerization


The realization of one-layer thick nano-devices is one of the great challenges of today nanotechnology. By exploiting the molecule-molecule and molecule-substrate interactions it is possible to create self-assembled 2D structures. Halogenated molecules can be further manipulated and form extended π-conjugated polymer by Ullmann reaction.

Small differences in the self-assembling building blocks, such as the used substrate or halogen (Fig. 1), affect the reaction pathway as well as the final polymer structure. In order to be able to engineer the polymerization result, it is necessary an increased understanding of the parameters that affect the process.

During the last decade, our group used a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy and density functional theory to understand the role of all the parameters involved in the reaction, in addition to characterize the material properties, such as the band-gap and the k-dispersion and study the reaction kinetic and mechanism involved in the polymerization.

The final goal of our group is get insights on the on-surface polymerization to realize extended 2D polymeric domain, to then use them for the realization of electronic devices.


Group members:

  • Fabrizio De Marchi
  • Maryam Ebrahimi
  • Gianluca Galeotti
  • Penghui Ji

Selected Publications:

  • G. Galeotti, M. Di Giovannantonio, J. Lipton-Duffin, M. Ebrahimi, S. Tebi, A. Verdini, L. Floreano, Y. Fagot-Revurat, D. Perepichka, F. Rosei, and G. Contini. The role of halogens in on-surface Ullmann polymerization. Faraday Discussions, 204, 453, 2017 (PDF).
  • M. Di Giovannantonio, M. Tomellini, J. Lipton-Duffin, G. Galeotti, M. Ebrahimi, A. Cossaro, A. Verdini, N. Kharche, V. Meunier, G. Vasseur, Y. Fagot-Revurat, D. Perepichka, F. Rosei, and G. Contini. Mechanistic Picture and Kinetic Analysis of Surface-Confined Ullmann Polymerization. Journal of the American Chemical Society, 138, 16696−16702, 2016 (PDF).
  • G. Vasseur, Y. Fagot-Revurat, M. Sicot, B. Kierren, L. Moreau, D. Malterre, L. Cardenas, G. Galeotti, J. Lipton-Duffin, F. Rosei, M. Di Giovannantonio, G. Contini, F. B. P. Le Fèvre, L. Liang, V. Meunier, and D. Perepichka. Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires. Nature Communications, 7, 2016 (PDF).
  • R. Gutzler, L. Cardenas, J. Lipton-Duffin, M. El Garah, L. E. Dinca, C. E. Szakacs, C. Fu, M. Gallagher, M. Vondracek, M. Rybachuk, D. F. Perepichka, and F. Rosei. Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver. Nanoscale, 6, 2660, 2014 (PDF).
  • M. Di Giovannatonio, M. El Garah, J. Lipton-Duffin, V. Meunier, L. Cardenas, Y. Fagot-Revurat, A. Cossaro, Dimitrii F. Perepichka A. Verdini, F. Rosei, and G. Contini. Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization. ACS Nano, 7, 8190–8198, 2013 (PDF).
  • L. Cardenas, R. Gutzler, J. Lipton-Duffin, J. L. Brusso, L. E. Dinca, M. Vondracek, Y. Fagot-Revurat, D. Malterre, F. Rosei, and D. F. Perepichka. Synthesis and electronic structure of a two dimensional π-conjugated polythiophene. Chemical Science, 4, 3263, 2013 (PDF).
  • J. A. Lipton-Duffin, J. A. Miwa, M. Kondratenko, F. Cicoira, B. G. Sumpter, V. Meunier, D. F. Perepichka, and F. Rosei. Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction. Proceedings of the National Academy of Sciences of the United States of America, 107, 11200–11204, 2010 (PDF).
  • J. A. Lipton-Duffin, O. Ivasenko, D. F. Perepichka, and F. Rosei. Synthesis of Polyphenylene Molecular Wires by Surface-Confined Polymerization. Small, 5, 592–597, 2009 (PDF).
  • D. F. Perepichka, and F. Rosei. CHEMISTRY Extending Polymer Conjugation into the Second Dimension. Science, 323, 216–217, 2009 (PDF).