Description du sujet de thèse

1. Keywords
Molecular electrochemistry, organometallic catalysis, electrosynthesis, coupling reactions.

2. Context
To limit the use of fossil-based energy and material resources in chemical production, the electrification of synthesis pathways offers a promising approach. This development introduces electrosynthesis (i.e. the creation of chemical bonds using electricity) as a key technology. The reach of this technology depends on the development of efficient catalysts adapted to electrosynthesis conditions – electrocatalysts. In this context, our team is developing original strategies to deploy electrocatalysis in synthesis. In particular, we are exploring these strategies for the functionalisation of organic skeletons, notably with renewable and abundant synthons, to generate higher value-added products.

3. Topic
This PhD subject aims to develop a molecular electrocatalysis approach for reductive couplings between multiple bonds of unsaturated substrates and building blocks for functionalisation. The topic will involve the rational design of transition metal complexes (e.g. Ni polypyridines) as electrocatalysts, building on results in hydrogenation previously described by the team. The reactions of interest will be more specifically electroreductive couplings between organic unsaturations, particularly alkynes/alkenes, carbonyls or nitriles, and reducible synthons, such as aldehydes and carbon or nitrogen oxides.

4.Methodologies
The work will begin with the synthesis of ligands and transition metal complexes and the associated molecular characterisations (NMR, IR, MS). Advanced electrochemical studies will then be carried out to evaluate the redox properties of these complexes and their reactivity in the reactions of interest (voltammetry, electrolysis, and possibly spectroelectrochemistry) and thus identify the best candidate catalysts. The application of these electrocatalysts for reactions of interest will then be studied through electrolysis campaigns and the coupling products obtained will be isolated and characterised by spectroscopic and chromatographic methods.

5. Required skills
Excellent knowledge and skills in molecular chemistry (organic, organometallic) in terms of synthesis, characterisation and properties (reactivity, physicochemical properties).
Proficiency in chemical handling under inert atmosphere.
Interest or experience in electrochemistry.

6. Skills and knowledge developed during the PhD
Molecular synthesis (organic, coordination complexes) and identification methods (NMR, GC/MS, HRMS).
Reactivity of organometallic species.
Electrochemistry of molecular compounds (voltammetry, electrolysis, spectro-electrochemistry).
Formatting and presentation of results in conferences and scientific articles.
Project work and scientific collaborations.

Contexte de travail

The successful candidate (M/F) will join the Molecular ElectroCatalysis for Synthesis and Energy (MeCSE) team within the Laboratoire d'Innovation Moléculaire et Applications (LIMA UMR 7042).
The thesis project will be supervised by Dr Nicolas Kaeffer within the MeCSE team.
The work will be carried out at the Strasbourg site of the laboratory (Cronenbourg Campus).
The doctoral school for this thesis is the Doctoral School of Chemical Sciences - ED222 (Unistra/UHA).

The MeCSE team is interested in the use of sustainable resources for the design of chemical products. The strategies implemented by the team aim to combine renewable electricity and abundant synthons in chemical conversions of interest for energy synthesis and storage. The team's activity focuses more specifically on the development, at the molecular level, of suitable and efficient electrocatalytic systems for the electrification of these transformations.
The MeCSE team has the necessary expertise and methodologies to cover the key aspects of the project (synthesis, electrochemistry, characterisation). In addition, the technical facilities and platforms available at the UMR (physical chemistry, analytics) provide access to more advanced characterisation techniques, which are extremely valuable for the studies involved. The research will also benefit from an extremely stimulating scientific environment within the UMR, whose work in molecular chemistry is widely recognised.
Finally, the team's activity is well identified at national and international level, with numerous connections in the field of research, which could lead to collaborations during the thesis.

Le poste se situe dans un secteur relevant de la protection du potentiel scientifique et technique (PPST), et nécessite donc, conformément à la réglementation, que votre arrivée soit autorisée par l'autorité compétente du MESR.

Contraintes et risques

The project will take place in a chemistry laboratory and will involve the synthesis and characterisation of organic and organometallic chemicals. The risks are therefore those associated with working in a chemistry laboratory and handling chemical compounds. These risks have been identified and are covered by a prevention plan at the UMR and team level. In addition, the collective and individual protective equipments necessary to deal with these risks is available in the laboratory.