A theoretical-guided design concept aiming to achieve highly efficient unidirectional charge transfer and multi-charge separation upon successive photoexcitation for light-harvesting dyes in the scope of supramolecular photocatalysts is presented. Four 4H-imidazole-ruthenium(ii) complexes incorporating a biimidazole-based electron-donating ligand sphere have been designed based on the well-known 4H-imidazole-ruthenium(ii) polypyridyl dyes. The quantum chemical evaluation, performed at the density functional and time-dependent density functional level of theory, revealed extraordinary unidirectional charge transfer bands from the near-infrared to the ultraviolet region of the absorption spectrum upon multi-photoexcitation. Spectro-electrochemical simulations modeling photoexcited intermediates determined the outstanding multi-electron storage capacity for this novel class of black dyes. These remarkable photochemical and photophysical properties are found to be preserved upon site-specific protonation rendering 4H-imidazole-ruthenium(ii) biimidazole dyes ideal for light-harvesting applications in the field of solar energy conversion.