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Chiral transition-metal complexes are of interest in many fields ranging fromasymmetric catalysis and molecular materials science to optoelectronicapplications or fundamental physics including parity violation effects. Wepresent here a combined theoretical and experimental investigation of gas-phasevalence-shell photoelectron circular dichroism (PECD) on the challengingopen-shell ruthenium(iii)-tris-(acetylacetonato) complex, Ru(acac)$_3$.Enantiomerically pure $\Delta$- or $\Lambda$-Ru(acac)$_3$, characterized byelectronic circular dichroism (ECD), were vaporized and adiabatically expandedto produce a supersonic beam and photoionized by circularly-polarized VUV lightfrom the DESIRS beamline at Synchrotron SOLEIL. Photoelectron spectroscopy(PES) and PECD experiments were conducted using a double imaging electron/ioncoincidence spectrometer, and compared to density functional theory (DFT) andtime-dependent DFT (TDDFT) calculations. The open-shell character ofRu(acac)$_3$, which is not taken into account in our DFT approach, is expectedto give rise to a wide multiplet structure, which is not resolved in our PESsignals but whose presence might be inferred from the additional strikingfeatures observed in the PECD curves. Nevertheless, the DFT-based assignment ofthe electronic bands leads to the characterisation of the ionized orbitals. Inline with other recent works, the results confirm that PECD persistsindependently on the localization and/or on the achiral or chiral nature of theinitial orbital, but is rather a probe of the molecular potential as a whole.Overall, the measured PECD signals on Ru(acac)$_3$, a system exhibiting D$_3$propeller-type chirality, are of similar magnitude compared to those onasymmetric-carbon-based chiral organic molecules which constitute the vastmajority of species investigated so far, thus suggesting that PECD is auniversal mechanism, inherent to any type of chirality.

Valence-shell photoelectron circular dichroism of ruthenium(iii)-tris-(acetylacetonato) gas-phase enantiomers