Enhancing Haloarene Coupling Reaction Efficiency on an Oxide Surface by Metal Atom Addition

Abadia, Mikel ; Piquero-Zulaica, Ignacio ; Brede, Jens ; Verdini, Alberto ; Floreano, Luca ; Barth, Johannes V. ; Lobo-Checa, Jorge ; Corso, Martina ; Rogero, Celia

Resumen: The bottom-up synthesis of carbon-based nanomaterials directly on semiconductor surfaces allows for the decoupling of their electronic and magnetic properties from the substrates. However, the typically reduced reactivity of such nonmetallic surfaces adversely affects the course of these reactions. Here, we achieve a high polymerization yield of halogenated polyphenyl molecular building blocks on the semiconducting TiO2(110) surface via concomitant surface decoration with cobalt atoms, which catalyze the Ullmann coupling reaction. Specifically, cobalt atoms trigger the debromination of 4,4″-dibromo-p-terphenyl molecules on TiO2(110) and mediate the formation of an intermediate organometallic phase already at room temperature (RT). As the debromination temperature is drastically reduced, homocoupling and polymerization readily proceed, preventing presursor desorption from the substrate and entailing a drastic increase of the poly-para-phenylene polymerization yield. The general efficacy of this mechanism is shown with an iodinated terphenyl derivative, which exhibits similar dehalogenation and reaction yield.

Idioma: Inglés

DOI: 10.1021/acs.nanolett.3c04111

Año: 2024

Publicado en: Nano Letters 24, 6 (2024), 1923-1930
ISSN: 1530-6984

Financiación: info:eu-repo/grantAgreement/ES/MCIU/PID2020-114252GB-I00
Financiación: info:eu-repo/grantAgreement/EUR/MCIU/TED2021-130292B-C42
Financiación: info:eu-repo/grantAgreement/EUR/MCIU/TED2021-132388B-C43

Tipo y forma: Article (Published version)