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Cyclometalated complexes of iridium(III) can be used as dyes in solar cells, where they interact with an iodine-containing redox mediator. The study of these components in the liquid phase seems to be a difficult task while in the solid state, assuming the same nature of the charge transfer processes, it is rather easy to inspect these components by a powerful single-crystal X-ray analysis. For this purpose, cyclometalated iridium(III) complexes based on benzimidazole ligands containing halogen substituents combined with polyiodide anions of various architecture were selected.