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Volume 204, 2017
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The role of halogens in on-surface Ullmann polymerization

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Ullmann coupling is the most common approach to form surface-confined one- and two-dimensional conjugated structures from haloaryl derivatives. The dimensions of the formed nanostructures can be controlled by the number and location of halogens within the molecular precursors. Our study illustrates that the type of halogen plays an essential role in the design, orientation, and extent of the surface-confined organometallic and polymeric nanostructures. We performed a comparative analysis of five 1,4-dihalobenzene molecules containing chlorine, bromine, and iodine on Cu(110) using scanning tunneling microscopy, fast-X-ray photoelectron and near edge X-ray absorption fine structure spectroscopies. Our experimental data identify different molecular structures, reaction temperatures and kinetics depending on the halogen type. Climbing image nudged elastic band simulations further clarify these observations by providing distinct diffusion paths for each halogen species. We show that in addition to the structure of the building blocks, the halogen type has a direct influence on the morphology of surface-confined polymeric structures based on Ullmann coupling.

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09 Mar 2017
30 Mar 2017
First published
06 Apr 2017

Faraday Discuss., 2017,204, 453-469
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The role of halogens in on-surface Ullmann polymerization

G. Galeotti, M. Di Giovannantonio, J. Lipton-Duffin, M. Ebrahimi, S. Tebi, A. Verdini, L. Floreano, Y. Fagot-Revurat, D. F. Perepichka, F. Rosei and G. Contini, Faraday Discuss., 2017, 204, 453
DOI: 10.1039/C7FD00099E

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