A series of five ruthenium complexes containing triphenyl phosphine groups known to enhance both cellular penetration and photoinduced ligand exchange, cis-[Ru(bpy)₂(P(p-R-Ph)₃)(CH₃CN)]²⁺, where bpy = 2,2'-bipyridine and P(p-R-Ph)₃ represent para-substituted triphenylphosphine ligands with R = -OCH₃ (1), -CH₃ (2) -H (3), -F (4), and -CF₃ (5), were synthesized and characterized. The photolysis of 1-5 in water with visible light (λ _irr ≥ 395 nm) results in the substitution of the coordinated acetonitrile with a solvent molecule, generating the corresponding aqua complex as the single photoproduct. A 3-fold variation in quantum yield was measured with 400 nm irradiation, Φ ₄₀₀, where 1 is the most efficient with a Φ ₄₀₀ = 0.076(2), and 5 the least photoactive complex, with Φ ₄₀₀ = 0.026(2). This trend is unexpected based on the red-shifted metal-to-ligand charge transfer (MLCT) absorption of 1 as compared to that of 5, but can be correlated to the substituent Hammett para parameters and pK _a values of the ancillary phosphine ligands. Complexes 1-5 are not toxic towards the triple negative breast cancer cell line MDA-MB-231 in the dark, but 3 and 5 are >4.2 and >19-fold more cytotoxic upon irradiation with blue light, respectively. A number of experiments point to apoptosis, and not to necrosis or necroptosis, as the mechanism of cell death by 5 upon irradiation. These findings provide a foundation for understanding the role of phosphine ligands on photoinduced ligand substitution and show the enhancement afforded by -CF₃ groups on photochemotherapy, which will aid the future design of photocages for photochemotherapeutic drug delivery.

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