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Sauaia MG, de Lima RG, Tedesco AC, da Silva RS: Nitric oxide production by visible light irradiation of aqueous solution of nitrosyl ruthenium complexes. Inorg Chem. 2005 Dec 26;44(26):9946-51. [Ru (II) L (NH (3))(4)(pz) Ru (II)(bpy)(2)(NO)](PF (6))(5) (L is NH (3), py, or 4-acpy) was prepared with good yields in a straightforward way by mixing an equimolar ratio of cis-[Ru (NO (2))(bpy)(2)(NO)](PF (6))(2), sodium azide (NaN (3)), and trans-[RuL (NH (3))(4)(pz)] (PF (6))(2) in acetone. These binuclear compounds display nu (NO) at ca. 1945 cm (-)(1), indicating that the nitrosyl group exhibits a sufficiently high degree of nitrosonium ion (NO (+)). The electronic spectrum of the [Ru (II) L (NH (3))(4)(pz) Ru (II)(bpy)(2)(NO)](5+) complex in aqueous solution displays the bands in the ultraviolet and visible regions typical of intraligand and metal-to-ligand charge transfers, respectively. Cyclic voltammograms of the binuclear complexes in acetonitrile give evidence of three one-electron redox processes consisting of one oxidation due to the Ru (2+/3+) redox couple and two reductions concerning the nitrosyl ligand. Flash photolysis of the [Ru (II) L (NH (3))(4)(pz) Ru (II)(bpy)(2)(NO)](5+) complex is capable of releasing nitric oxide (NO) upon irradiation at 355 and 532 nm. NO production was detected and quantified by an amperometric technique with a selective electrode (NOmeter). The irradiation at 532 nm leads to NO release as a consequence of a photoinduced electron transfer. All species exhibit similar photochemical behavior, a feature that makes their study extremely important for their future application in the upgrade of photodynamic therapy in living organisms. |
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