Thesis proposal
Earth-abundant metal complexes supported by iminophosphorane ligand for application in optics and/or catalysis
Keywords: Coordination chemistry, Noble metal alternative, Iminophosphorane ligand, optics, catalysis, sustainable chemistry.
Contact: audrey.auffrant@polytechnique.edu
The mission will be to synthesize divalent lanthanide complexes, particularly samarium(II) and thulium(II) complexes, supported by ligands of varied denticity (bidentate, tripodal, cyclopentadienyl-type ligands). The reactivity of these complexes will be studied towards CO with the objective to induce CO reductive dimerization leading into ethynediolate Ln-OCCO-Ln motifs. Preliminary results have shown the high reactivity of this kind of arrangements in the presence of CO2, resulting in an original functionalization strategy of CO and CO2. The first objective of this PhD project is to study this new functionalization reactivity from a stoichiometric point of view and to characterize the newly-formed products. A second objective will consist in the establishment of methodologies allowing to go towards (electro)catalytic transformations with these systems.
The mission will be to synthesize complexes of f-elements (lanthanides, uranium and thorium) with ligands developed in the laboratory. The synthesis of suitable ligands, large aromatic ligands, will be carried out in collaboration, laboratory researcher and specialist in organic synthesis. The PhD student will synthesize the ligands and complexes with the f-elements, and characterize them with the support of PhD and post-doc students working on the subject, using multiple methods including X-ray diffraction, magnetism, EPR, NMR, UV-Vis-NIR and infrared/Raman spectroscopy. In collaboration with the other members of the group, the PhD student will ensure that the synthesis room is properly maintained and operated, by the recommendations of the funding bodies and laboratory management, and may be required to supervise undergraduate students.
- Develop organic synthesis of broad aromatic ligands
- Synthesize lanthanide and uranium complexes with organic ligands in inert media.
- Characterize complexes using routine X-ray diffraction, magnetism, EPR, NMR, UV-Vis-NIR and infrared/Raman spectroscopies.
- Participate in non-routine complex characterizations: magnetism, EPR and XAS.
- Participate in the group's international collaborations, visiting foreign laboratories in the USA.
- Monitor scientific developments related to the research topic.
- Prepare written reports and communicate results according to the recommendations proposed by the funder.
- Participate in research seminars.
- Write up research results in scientific documents suitable for patent registration or publication.
- Supervise masters and bachelor students in the research group.
- Ensure the proper maintenance and operation of the synthesis rooms by the recommendations of the funding bodies and laboratory management.
- Participate in the maintenance of research group and laboratory equipment.
