On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111).

DFT Polyaniline coupling reactions nc-AFM/STM on-surface synthesis

Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
14 Dec 2020
Historique:
received: 17 07 2020
pubmed: 8 8 2020
medline: 8 8 2020
entrez: 8 8 2020
Statut: ppublish

Résumé

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.

Identifiants

pubmed: 32761699
doi: 10.1002/anie.202009863
pmc: PMC7116460
mid: EMS105440
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

23220-23227

Subventions

Organisme : European Research Council
ID : 610256
Pays : International
Organisme : Ministerio de Economía, Industria y Competitividad, Gobierno de España
ID : MAT2017-85089-C2-1-R
Organisme : FP7 Ideas: European Research Council
ID : 610256
Organisme : H2020 Future and Emerging Technologies
ID : 881608

Informations de copyright

© 2020 The Authors. Published by Wiley-VCH GmbH.

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Auteurs

Nerea Ruiz Del Árbol (N)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Carlos Sánchez-Sánchez (C)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Gonzalo Otero-Irurueta (G)

Centre for Mechanical Technology and Automation (TEMA), University of Aveiro, 3810-193, Aveiro, Portugal.

José I Martínez (JI)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Pedro L de Andrés (PL)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Ana C Gómez-Herrero (AC)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Pablo Merino (P)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Marten Piantek (M)

Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, 50009, Zaragoza, Spain.

David Serrate (D)

Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, 50009, Zaragoza, Spain.

Paolo Lacovig (P)

Elettra-Sincrotrone Trieste S.C.p.A., Strada Statale 14 km 163.5, 34149, Trieste, Italy.

Silvano Lizzit (S)

Elettra-Sincrotrone Trieste S.C.p.A., Strada Statale 14 km 163.5, 34149, Trieste, Italy.

José Alemán (J)

Organic Chemistry Department, Módulo 1, Universidad Autónoma de Madrid, 28049, Madrid, Spain.

Gary J Ellis (GJ)

Polymer Physics Group, Institute of Polymer Science and Technology (ICTP-CSIC), Juan de la Cierva 3, 28006, Madrid, Spain.

María F López (MF)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

José A Martín-Gago (JA)

ESISNA Group, Materials Science Factory, Institute of Materials Science of Madrid (ICMM-CSIC), Sor Juana Inés de la Cruz 3, 28049, Madrid, Spain.

Classifications MeSH