On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111) |
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Authors: | Nerea Ruiz del Árbol Carlos Sánchez-Sánchez Gonzalo Otero-Irurueta José I Martínez Pedro L de Andrés Ana C Gómez-Herrero Pablo Merino Marten Piantek David Serrate Paolo Lacovig Silvano Lizzit José Alemán Gary J Ellis María F López José A Martín-Gago |
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Institution: | 1. ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049 Madrid, Spain;2. Centre for Mechanical Technology and Automation (TEMA), University of Aveiro, 3810-193 Aveiro, Portugal;3. Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, 50009 Zaragoza, Spain;4. Elettra—Sincrotrone Trieste S.C.p.A., Strada Statale 14 km 163.5, 34149 Trieste, Italy;5. Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049 Madrid, Spain;6. Polymer Physics Group, Institute of Polymer Science and Technology (ICTP-CSIC), Juan de la Cierva 3, 28006 Madrid, Spain |
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Abstract: | On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures. |
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Keywords: | coupling reactions DFT nc-AFM/STM on-surface synthesis Polyaniline |
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