The solution-phase photochemistry of the [FeFe] hydrogenase subsite model (μ-S(CH2)3S)Fe2(CO)4(PMe3)2 has been studied using ultrafast time-resolved infrared spectroscopy supported by density functional theory calculations. In three different solvents, n-heptane, methanol, and acetonitrile, relaxation of the tricarbonyl intermediate formed by UV photolysis of a carbonyl ligand leads to geminate recombination with a bias towards a thermodynamically less stable isomeric form, suggesting that facile interconversion of the ligand groups at the Fe center is possible in the unsaturated species. In a polar or hydrogen bonding solvent, this process competes with solvent substitution leading to the formation of stable solvent adduct species. The data provide further insight into the effect of incorporating non-carbonyl ligands on the dynamics and photochemistry of hydrogenase-derived biomimetic compounds.

Solution-phase photochemistry of a [FeFe]hydrogenase model compound: evidence of photoinduced isomerisation.

Cathodic and anodic deposition of FeS2 thin films and their application in electrochemical reduction and amperometric sensing of H2O2

Investigation of the Ultrafast Dynamics Occurring during Unsensitized Photocatalytic H2 Evolution by an [FeFe]-Hydrogenase Subsite Analogue

Ab initio study of ligand dissociation/exchange and the hydrogen production process of the Co(dmgH)2(py)Cl cobaloxime in the acetonitrile-water solvent

Annabella Selloni

Papers

Electrocatalyst design from first principles: A hydrogen-production catalyst inspired by nature