Two diimine-bridged Ru(II),Mn(I) complexes with a [(bpy)Ru(BL)Mn(CO)Br] architecture, where bpy = 2,2'-bipyridine and BL = 2,3-bis(2-pyridyl)pyrazine (dpp; Ru(dpp)Mn) or 2,2'-bipyrimidine (bpm; Ru(bpm)Mn), were designed to both dissociate multiple equivalents of CO and produce O when irradiated with visible light. Analysis of the complexes by Fourier transform infrared (FTIR) spectroscopy and cyclic voltammetry suggest a stronger π-accepting ability for bpm compared to that of dpp. Both complexes absorb light throughout the UV and visible regions with lowest energy absorption bands comprising overlapping Ru(dπ)→BL(π*) and Mn(dπ)→BL(π*) singlet metal-to-ligand charge transfer (MLCT) and Br(p)→dpp(π*) singlet halide-to-ligand charge transfer (XLCT) transitions. This lowest energy band is centered at 510 nm (ε = 12 000 Mcm) for Ru(dpp)Mn and 553 nm (ε = 3240 Mcm) for Ru(bpm)Mn, and the absorption band extends to nearly 700 nm in each case. Irradiation with visible light (both 470 and 627 nm) releases all three CO ligands, as observed by a combination of UV-vis, FTIR, and gas chromatography. The exchange of the first CO ligand with a solvent molecule occurs more efficiently for Ru(dpp)Mn (Φ = 0.22 ± 0.03 in HO; 0.37 ± 0.06 in CHCN) than for Ru(bpm)Mn (Φ = 0.049 ± 0.008 in HO and 0.16 ± 0.03 in CHCN), and the CO dissociation efficiency is unaffected by irradiation wavelength. The differences between Ru(dpp)Mn and Ru(bpm)Mn are proposed to result from the variation in electron density distribution across each formally reduced BL in the Mn(dπ)→BL(π*) MLCT excited state based on the nature of BL. Exhaustive photolysis causes the decomplexation of oxidized Mn(II), and the resulting [(bpy)Ru(BL)] complexes produce O with quantum yields (Φ) of 0.37 ± 0.03 and 0.16 ± 0.01 for Ru(dpp) and Ru(bpm), respectively, with 460 nm irradiation. This bimetallic architecture presents the opportunity to use visible light to codeliver both CO and O, both of which have biological relevance in photoactivated therapeutics, with spatiotemporal control.

Carbon monoxide (CO) is shown to enhance the sensitivity of cancer cells to generate reactive oxygen species such as singlet oxygen ( 1 O 2 ) from chemotherapeutics and reduce the drug resistance. Herein, we introduced two Mn-based photoactivated CO releasing molecules conjugated with an emissive BODIPY (BDP) moiety with a general formula of Mn(CO) 3 (bpy-R-BDP)Br (R = H or I), labeled as Mn-bpy-H-BDP and Mn-bpy-I-BDP. While both complexes release CO with visible light, Mn-bpy-I-BDP releases CO and produces 1 O 2 from a single molecule. In addition to 1 O 2 generation, iodination of BDP red shifts the absorption of Mn-bpy-I-BDP further into the visible region and significantly increases the dark stability of the complex. Cyclic voltammetry and density functional theory (DFT) calculations suggest a Mn-based highest occupied molecular orbital (HOMO) and a BDP-based lowest unoccupied molecular orbital (LUMO) in these complexes. However, time-dependent DFT calculations suggest that the HOMO − 2(π BDP ) → LUMO(π BDP * ) is the main optical transition upon excitation with visible light in both complexes. The presence of a phosphorescence peak from the triplet excited state of bpy-I-BDP in both the free ligand and its Mn complex at 77 K was used as additional evidence for 1 O 2 production. We also probed formation of photo-intermediates and products during photolysis with Fourier-transform infrared, 1 H NMR, emission, and absorption experiments and DFT calculations.

A Ru(II) intercalating complex capped with a Mn(I) photoCORM allows for a new mode of DNA intercalator delivery. The steric bulk of the Mn(I) photoCORM inhibits intercalation in the dark,...