The interest in chromium(III) complexes has been renewed over the past decade for the design of efficient earth-abundant phosphorescent red-to-near-infrared spin-flip emitters and photocatalysts with long excited state lifetimes. In this context, we report the energy tuning of spin-flip excited states based on heteroleptic bis(tridentateare obtained via a novel synthetic approach toward the required intermediate labile triflato complexes Cr(L X )(OTf) 3 (2 X ) from the respective chlorido precursors CrCl 3 (L X ) (1 X ) using trimethylsilyl trifluoromethanesulfonate. Spin-flip energies were experimentally detected by vis/near-infrared absorption and emission spectroscopy as well as computationally derived by multireference calculations. Together with the known homoleptic molecular ruby complexes, the three resulting series of luminescent complexes [3 X,X ] 3+ /[3 X,Y ] 3+ /[3 Y,Y ] 3+ allow delineation of an additive nephelauxetic effect of the ligands with chromium(III) ions and thus prediction of spin-flip emission energies of derived molecular rubies.