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? Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor.


ABSTRACT: Surface-confined dehalogenation reactions are versatile bottom-up approaches for the synthesis of carbon-based 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 TiO2(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 tight-binding calculations identify a highly dispersive band characteristic of a substantial overlap between the precursor's ? 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.

SUBMITTER: Vasseur G 

PROVIDER: S-EPMC4858753 | biostudies-literature | 2016 May

REPOSITORIES: biostudies-literature

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Π Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor.

Vasseur Guillaume G   Abadia Mikel M   Miccio Luis A LA   Brede Jens J   Garcia-Lekue Aran A   de Oteyza Dimas G DG   Rogero Celia C   Lobo-Checa Jorge J   Ortega J Enrique JE  

Journal of the American Chemical Society 20160426 17


Surface-confined dehalogenation reactions are versatile bottom-up approaches for the synthesis of carbon-based 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 TiO2(110) via a dehalogenative ho  ...[more]

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