Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Ruthenium dyes incorporating a 4<jats:italic>H</jats:italic>‐imidazole chromophore as a ligand exhibit a spectrally broad absorption in the UV/Vis region. Furthermore, they show the ability to store two electrons within the 4<jats:italic>H</jats:italic>‐imidazole ligand. These features render them promising molecular systems, for example, as inter‐ or intramolecular electron relays. To optimize the structures with respect to their electron‐storage capability, it is crucial to understand the impact of structural changes accompanying photoinduced charge transfer in the electronic intermediates of multistep electron‐transfer processes. The photophysical properties of these (reactive) intermediates might impact the function of the molecular systems quite substantially. However, the spectroscopic study of short‐lived intermediates in stepwise multielectron‐transfer processes is experimentally challenging. To this end, this contribution reports on the electrochemical generation of anions identical to intermediate structures and their spectroscopic characterization by in situ resonance Raman and UV/Vis spectroelectrochemistry and computational methods. Thereby, an efficient two‐electron pathway to the 4<jats:italic>H</jats:italic>‐imidazole electron‐accepting ligand is identified.</jats:p>