Fortunately, the ground-state reduction potential, Ered, could be acquired in all four solvents when solubility allowed; indeed, all electrochemistry solutions were homogeneous, except for Eosin Y in THF, which was a suspension. The redox potentials versus SCE are collated in The Ered values were generally found to also shift cathodically with increasing solvent polarity (Table ), suggesting that polar media serve to render the PC given that the UV-Vis absorption spectrum is insensitive to solvent polarity (vide infra), which implies that all solvents contain the same structural form of Eosin Y. As solvent polarity increases, the energy gap between the ground state oxidation and reduction potentials, ΔE, was generally found to decrease (Table ). However, as stipulated previously, we can only cautiously assign this trend given that Eox could typically only be determined in two out of four of the solvents. In order to understand the origins of the effect of solvent on the electrochemical properties of the PC we conducted DFT studies to predict the redox properties of the PCs. As a first step, the IP and EA of each PC was calculated using DFT via the delta-SCF approach in each of the four solvents of interest (Figure , Table ). Each solvent was modelled implicitly, using the integral equation formalism polarizable continuum model (IEF-PCM) and the default dielectric constant for each solvent as implemented in Gaussian 16. For all the DFT results, the organometallic complexes were modelled as single species (i.e., without their outer-sphere counter anion), due to the difficulty of optimising the interaction with a loosely bound ligand.