X-ray emission spectroscopy in liquid jets: A effective tool to probe valence and p -shells in organometallics and the influence of the solvation

In this combined experimental and theoretical work, we present state-of-the-art liquid jet experiments based on x-ray emission spectroscopy of the [Fe(CN)6]4- and [Fe(CN)6]3- molecular ions in the hard-x-ray energy range. The ab initio simulations of the valence-to-core and Kβ spectra reveal insights into the valence and metal's d-shells, respectively. These results open new perspectives for applying spectroscopy to organometallic complexes in order to disentangle and probe various environmental effects, including solvent interactions, pH variations, and ligand field influences and dynamical processes, such as charge transfer or photoinduced ligand exchange reactions such as photoaquation in solution.