Light activated drugs for cancer treatment is an important area of study as it can focus the cell damage to only the intended area of treatment and limit the damage to healthy tissues. A class of compounds called photoCORMs (photoactivated CO-releasing molecules) offers the spatiotemporal controlled delivery of CO. The use of CO as a therapy is currently under investigation and may provide a route to overcome resistance some chemotherapies currently experience. The combination of CO with other cytotoxic species such as singlet oxygen has the potential to act synergistically to increase the toxicity towards cancer cells. A common cytotoxic species, singlet oxygen, has been shown to be produced using Ru(II) polypyridyl complexes. A series of Ru(II),Mn(I) bimetallic complexes, [(bpy)2Ru(tpphz)Mn(CO)3(L)]n+ (where tpphz = tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]phenazine, where L = Br– , n = 2; or L = CH3CN, n = 3) are compared in their ability to combine these two therapeutic agents through a photochemical release of a singlet oxygen producer, [Ru(bpy)2(tpphz)]2+, and release of CO from the Mn(I) component. Infrared spectroscopy was used to monitor the release of up to three equivalents of CO when exposed to visible light, while absorption spectroscopy was used to monitor the release of the ruthenium photosensitizer. The ability of the Mn(I) photoCORM coordination to inhibit DNA intercalation of the tpphz ligand in the dark was investigated using relative viscosity. The inhibition of the intercalation was removed upon photolyzed release of the Mn(I) photoCORM. The synthesis, characterization, and photoinduced ligand dissociation of the Ru(II),Mn(I) bimetallic complexes will be presented.

Visible light activated DNA intercalation of Ru(II)(tpphz)Mn(I) bimetallic complexes

ACS Fall 2021

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