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π band dispersion along conjugated organic nanowires synthesized on a metal oxide semiconductor

AuthorsVasseur, Guillaume; Abadia, Mikel; Miccio, Luis A.; Brede, Jens; García-Lekue, Aran; Oteyza, D. G. de ; Rogero, Celia ; Lobo-Checa, Jorge ; Ortega, J. Enrique
Issue Date2016
PublisherAmerican Chemical Society
CitationJournal of the American Chemical Society 138(17): 5685-5692 (2016)
AbstractSurface-confined dehalogenation reactions are versatile bottom-up approaches for the synthesis of carbonbased nanostructures with predefined chemical properties. However, for devices generally requiring low-conductivity substrates, potential applications are so far severely hampered by the necessity of a metallic surface to catalyze the reactions. In this work we report the synthesis of ordered arrays of poly(p-phenylene) chains on the surface of semiconducting TiO(110) via a dehalogenative homocoupling of 4,4″- dibromoterphenyl precursors. The supramolecular phase is clearly distinguished from the polymeric one using low-energy electron diffraction and scanning tunneling microscopy as the substrate temperature used for deposition is varied. X-ray photoelectron spectroscopy of C 1s and Br 3d core levels traces the temperature of the onset of dehalogenation to around 475 K. Moreover, angle-resolved photoemission spectroscopy and tightbinding calculations identify a highly dispersive band characteristic of a substantial overlap between the precursor's π states along the polymer, considered as the fingerprint of a successful polymerization. Thus, these results establish the first spectroscopic evidence that atomically precise carbon-based nanostructures can readily be synthesized on top of a transition-metal oxide surface, opening the prospect for the bottom-up production of novel molecule-semiconductor devices.
Publisher version (URL)https://doi.org/10.1021/jacs.6b02151
Identifiersdoi: 10.1021/jacs.6b02151
e-issn: 1520-5126
issn: 0002-7863
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