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

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-amino-phenol 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.

Revealing Kinetics Process of Fast Charge‐Storage Behavior Associated with Potential in 2D Polyaniline

“…After the mutual transformation of polaron lattice and bipolarons, N element in the system will be existed at four states (–NH–, –NH ·+ –, –NH + = and –N=) and their corresponding standard binding energy positions are approximately 402.5, 401, 399.5, and 398.5 eV. [ 27 ] However, for PANI synthesized by standard process (without AMT), it would be dominated by –NH– and –NH ·+ –, that is, reduced amine and polaron. [ 28–30 ] The X‐Ray photoelectron spectroscopy (XPS) spectrum (Figure S2, Supporting Information) shows this conclusion very well.…”

Polyaniline based polymers in tissue engineering applications: a review

“…Manifold processing methods for conductive TE scaffolds based on PANi are available including electrospinning, 3D printing, thermally induced phase separation, and direct mixing, as well as less commonly chemical oxidative polymerization. A green approach by the Michael addition reaction has also been reported [65]. There are comprehensive publications available in the open literature, and for TE the fabrication methods may be broadly subdivided into three different groups, i.e.…”

On-surface synthesis of metal–organic frameworks: the critical role of the reaction conditions

“…In this work, we have selected para -aminophenol ( p -AP), a simple aromatic molecule with two functional groups (alcohol and amine, see lower inset in Fig. 1a) previously used in OSS, 27,28 as a precursor for growing two different 2D-MOFs on Cu(111) by rationally adjusting the synthesis protocol, evidencing the relevance of the reaction conditions on the final product. The two networks are a topological Kagome and a canonical honeycomb lattice, structures that are attracting increasing interest as they have been predicted to be potential organic topological insulators.…”