CE06 - Polymères, composites, physique et chimie de la matière molle

Polymeric Modular Platforms by Macromolecular Synthesis Involving Bis-carbene Building Blocks in Polymerization Reactions – CARBENOPOL

Submission summary

Singlet carbenes have witnessed tremendous developments in the past two decades, not only as ligands of transition metals, but also as organic catalysts both in molecular chemistry and in polymer synthesis. In contrast, their utility as true monomers has received very little attention. Here we propose new methodological approaches in macromolecular synthesis by exploiting the reactivity of peculiar singlet carbenes. Namely, acyclic aminoaryl bis-carbenes will serve as building blocks in key elementary reactions, including “carbene dimerization”, “carbene-metal coordination”, and “carbene insertion” in presence of difunctional monomer partners (e.g. disilanes, diboranes or diphosphanes). An important objective throughout the whole project is to rationalize the effects of a structural variation of the carbene precursors and experimental conditions on the reaction outcomes, and to elucidate the underlying reaction mechanisms. One specific objective relates to the dimerization reaction. As this process has a stereochemical impact on the configuration of the resulting olefin (Z vs. E), we aim at fostering a “programmable dimerization”, i.e. at achieving stereo-defined isomers, through a proper selection of reaction partners and reaction conditions.

The program will be implemented through 4 scientific WP’s. Polymerization experiments, chemical post-modification of pre-formed polymers, polymer characterization and valorization of some polymeric compounds elaborated will be performed at LCPO (partner 1, WP’s 1&4), synthesis of carbene precursors, silanes, boranes and phosphanes, and benchmark reactions involving carbenes will be assessed at ISM (partner 2, WP2), while calculations of geometrical structures, electronic, and photo-physical properties, as well as modeling of reaction pathways will be realized at IPREM (partner 3, WP3). The reactivity mapping of the different mono- and bis-aminoaryl carbenes will thus be appraised through combined experimental and theoretical studies. In particular, their nucleophilic and electrophilic character will be established, as it greatly influences their reactivity. These investigations will establish the foundations for polymerization reactions performed at LCPO (partner 1, WP1). Owing to the broad modularity of carbenes, a modular platform of polymers should be achieved, including p-conjugated amino-containing poly(phenylene vinylene) (PPV)-type polymers, main-chain organometallic polymers consisting of carbene-metal-carbene units, and hybrid polymers, such as polyaminosilanes, polyaminoboranes and polyaminophosphanes. The physico-chemical properties of the resulting polymeric frameworks will be tuned by a structural variation of the bis-carbenes through the use of a wide range of substrates. Moreover, the presence of tertiary amino side groups in all targeted polymers imparts additional synthetic options to tune the physico-chemical properties of final compounds, through selective chemical post-modification, e.g. by protonation, alkylation or oxidation reactions (partner 1, WP 4). Such post-treatments should lead to polymer derivatives showing different properties compared to the parent polymers. Finally, some of the macromolecular compounds envisioned in this project will be integrated as active components in sensors or in optoelectronic devices, such as OLEDS, or OFET or sensors.

Overall, the ambition of this proposal not only embraces fundamental developments, but also more application-oriented aspects, through innovative methodological approaches in polymer chemistry and access to modular macromolecular platforms.

Project coordination

Daniel Taton (LABORATOIRE DE CHIMIE DES POLYMERES ORGANIQUES)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

LCPO LABORATOIRE DE CHIMIE DES POLYMERES ORGANIQUES
IPREM INSTITUT DES SCIENCES ANALYTIQUES ET DE PHYSICO-CHIMIE POUR L'ENVIRONNEMENT ET LES MATERIAUX
ISM INSTITUT DES SCIENCES MOLECULAIRES

Help of the ANR 477,671 euros
Beginning and duration of the scientific project: October 2019 - 42 Months

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