Trifluoromethyl substitution enhances photoinduced activity against breast cancer cells but reduces ligand exchange in Ru(ii) complex.

A series of five ruthenium complexes containing triphenyl phosphine groups known to enhance both cellular penetration and photoinduced ligand exchange, -[Ru(bpy)(P(-R-Ph))(CHCN)], where bpy = 2,2'-bipyridine and P(-R-Ph) represent -substituted triphenylphosphine ligands with R = -OCH (), -CH () -H (), -F (), and -CF (), were synthesized and characterized. The photolysis of in water with visible light ( ≥ 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, , where is the most efficient with a = 0.

Panchromatic dirhodium photocatalysts for dihydrogen generation with red light.

A series of three dirhodium complexes -[Rh(DPhB)(bncn)](BF) (, DPhB = diphenylbenzamidine; bncn = benzocinnoline), -[Rh(DPhTA)(bncn)](BF) (, DPhTA = diphenyltriazenide), and -[Rh(DPhF)(bncn)](BF) (, DPhF = ,'-diphenylformamidinate) shown to act as single-molecule photocatalysts for H production was evaluated. Complexes are able to generate H in the absence of any other catalyst in homogenous acidic solution upon irradiation with red light in the presence of the sacrificial electron donor BNAH (1-benzyl-1,4-dihydronicotinamide). The excited state of each complex is reductively quenched by BNAH, producing the corresponding one-electron reduced complex.