Université Paul Sabatier - Bat. 3R1b4 - 118 route de Narbonne 31062 Toulouse Cedex 09, France


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Home > Teams > Theoretical and Computational Photochemistry (PTC) > Research projects > Photorelease of ligands in ruthenium complexes

Photorelease of ligands in ruthenium complexes

In collaboration with Sylvestre Bonnet’s group (Leiden University, Netherlands), we are working on the rationalization of photolabilization quantum yields in ruthenium complexes of biological interest.

We have shown that the 3MC surface was offering two minima, namely two structures sharing the same electronic configuration. These isomers are involved in the photolabilization of a thioether ligand. We have proposed that a first 3MC minimum, with a reasonably elongated Ru-S distance of ca. 3 angstroms, could bring the system back to its initial state, while a second 3MC isomer, almost degenerate but almost pentacoordinated (Ru-S ca. 4 angstroms), would favor solvent attack and the departure of the sulfur ligand.

In collaboration with Paul Elliott’s group (University of Huddersfield, UK), we are also interested in mechanistic studies related to photolabilization of bidentate ligands, which are intrinsically more complex due to the difficulty to foresee the reaction coordinate. In this context we have identified new 3MC states that possess peculiar geometries: flattened hexacoordinated or truly pentacoordinated. This work has allowed us to refine our knowledge of the 3MC state region, and to propose a multistep mechanism for the formation of Elliott’s original κ-1 intermediate photoproduct.

This project has led to two publications :

Inorg. Chem. 2016, 55, 4448 link

PCCP 2017, 19, 27765 link