LCPQ / Université Toulouse 3
Téléphone : 05 61 55 64 88
Contact : isabelle.dixon@irsamc.ups-tlse.fr
Context : Rhenium(I) carbonyl complexes can be designed to release carbon monoxide under light irradiation.[1] Their air- and water-stability, combined with their biocompatibility,[2] make them great candidates for antimicrobial purposes.[3] Singlet oxygen sensitization has also been evidenced for such compounds,[1] which could potentiate the biological effect of CO. The current challenge is now to improve the visible light absorption properties of light-triggered CO releasing molecules (photoCORMs), while maintaining their excellent CO photoreleasing abilities. Objectives : In the framework of an experimental collaboration with Dr Suzanne Féry-Forgues (SPCMIB Toulouse, PANTHERA ANR project leader) and Pr Vincent Sol (PEIRENE Limoges), a computational postdoctoral researcher will design novel Re(I) complexes with red-shifted absorption properties and will rationalize their photoreactivity using methods based on density functional theory. The host team has the expertise to probe the topology of the potential energy surfaces (PES) of such complexes, in particular in the context of photoinduced ligand loss processes.[4] At the same time, a Ph.D. student will undertake the preparation and photophysical studies in the partner labs. The calculations will be performed on the local cluster or on the regional HPC facility (CALMIP). Roadmap : The aim of the theoretical contribution to the project is to assist in the design of potentially efficient complexes displaying the desired absorption properties and ability to sensitize 1O2, in order to minimize synthetic efforts. The absorption properties will be simulated using implicit solvent models and an orbital analysis will be conducted to rationalize the design. Photoreactivity and 1O2 sensitization will be probed on selected complexes by optimizing the relevant triplet excited states (3MLCT and 3MC), in order to assess their propensity towards energy transfer to 3O2 vs dissociative 3MC population, if thermally accessible. Additionally, energy barriers along the lowest triplet PES will be quantified using Nudged Elastic Band methods and/or transition state optimization, and key crossing points involved in nonradiative decay will be optimized. Skills : Ph.D. in the quantum chemistry of excited states, defended no earlier than 2020. Fluent English or French. Some knowledge of Python programming is desirable.
Contact : Dr Isabelle Dixon (dixon@irsamc.ups-tlse.fr), Dr Martial Boggio-Pasqua (boggio@irsamc.ups-tlse.fr).
Net salary ca. 2.300 €/month. The position should be available for 12 months from 01 Jan 2023. Applications should proceed through the dedicated CNRS website : https://emploi.cnrs.fr/
References : [1] Dalton Trans. 2021, 50, 1313–1323. [2] Dyes Pigm. 2021, 184, 108876. [3] Molecules 2022, 27, 539. [4] J. Mol. Model. 2016, 22: 384; Inorg. Chem. 2016, 55, 4448–4456; Phys. Chem. Chem. Phys. 2017, 19, 27765–27778; Molecules 2020, 25, 2613; Inorg. Chem. 2020, 59, 14679–14695; J. Phys. Chem. Lett. 2021, 12, 30, 7278–7284.