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Surface-mediated Assembly, Polymerization and Degradation of Thiophene-based Monomers

Abstract

Ullmann coupling of halogenated aromatics is widely used in on-surface synthesis of two-dimensional (2D) polymers and graphene nanoribbons. It stands out among other reactions for regioselective connecting aromatic monomers into 1D and 2D π-conjugated polymers, whose final structure and properties are determined by the initial building blocks. Thanks to their exceptional electronic properties, thiophene-containing monomers are frequently used for the synthesis of various conjugated materials. On the other hand, their use in on-surface polymerization is hampered by the possibility of ring opening when adsorbed on metal surfaces. In the present work, we mapped the temperature regime for these two competing reactions by investigating the adsorption of a thiophene-based prochiral molecule using scanning tunneling microscopy, X-ray photoelectron spectroscopy and density functional theory calculations. We followed the formation of organometallic (OM) networks, their evolution into covalent structures and the competition between C-C coupling and thiophene ring opening. The effect of surface reactivity was explored by comparing the adsorption on three (111) coinage metal substrates, namely Au, Ag and Cu. While outlining strategies to minimize the ring opening reaction, we found that the surface temperature during deposition is of paramount importance for the preparation of 2D OM networks, greatly enhancing the overall ordering of the product by depositing on hot Ag surface. Notably, the same protocol permits the creation of OM structures on the air-stable Au surface, thereby allowing the synthesis and application of 2D OM networks outside the ultra-high vacuum environment.

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Publication details

The article was received on 26 Nov 2018, accepted on 15 Apr 2019 and first published on 16 Apr 2019


Article type: Edge Article
DOI: 10.1039/C8SC05267K
Citation: Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY license
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    Surface-mediated Assembly, Polymerization and Degradation of Thiophene-based Monomers

    G. Galeotti, F. De Marchi, T. Taerum, L. Besteiro, M. El Garah, J. Lipton-Duffin, M. Ebrahimi, D. Perepichka and F. Rosei, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C8SC05267K

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