doi:10.1002/anie.202009863engRuiz del Árbol, N.Sánchez-Sánchez, C.Otero-Irurueta, G.Martínez, J.I.de Andrés, P.L.Gómez-Herrero, A.C.Merino, P.Piantek, M.Serrate, D.Lacovig, P.Lizzit, S.Alemán, J.Ellis, G.J.López, M.F.Martín-Gago, J.A.On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111)ART-2020-120593On-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.2020http://zaguan.unizar.es/record/9619410.1002/anie.202009863http://zaguan.unizar.es/record/96194oai:zaguan.unizar.es:96194info:eu-repo/grantAgreement/EC/FP7/610256/EU/Gas and Dust from the Stars to the Laboratory: Exploring the NanoCosmos/NANOCOSMOSinfo:eu-repo/grantAgreement/EC/H2020/785219/EU/Graphene Flagship Core Project 2/GrapheneCore2This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 785219-GrapheneCore2info:eu-repo/grantAgreement/EC/H2020/881603/EU/Graphene Flagship Core Project 3/GrapheneCore3This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No H2020 881603-GrapheneCore3info:eu-repo/grantAgreement/ES/MINECO/MAT2017-85089-C2-1-Rinfo:eu-repo/grantAgreement/ES/MINECO/RYC-2015-17730Angewandte Chemie (International ed.) 59, 11 (2020), 23220-23227byhttp://creativecommons.org/licenses/by/3.0/es/info:eu-repo/semantics/openAccess