Photochemical studies of cis-[Ru(bpy) 2 (4-bzpy)(CO)](PF 6 ) 2 and cis-[Ru(bpy) 2 (4-bzpy)(Cl)](PF 6 ): Blue light-induced nucleobase binding.

The ruthenium(II) compounds cis-[Ru(bpy)2 (4-bzpy)(CO)](PF6 )2 (I) and cis-[Ru(bpy)2 (4-bzpy)(Cl)](PF6 ) (II) (4-bzpy=4-benzoylpyridine, bpy=2,2'-bipyridine) were synthesized and characterized by spectroscopic and electrochemical techniques. The crystal structure of II was determined by X-ray diffraction. The photochemical behavior of I in aqueous solution shows that irradiation with ultraviolet light (365nm) releases both CO and 4-bzpy leading to the formation of the cis-[Ru(bpy)2 (H2 O)2 ]2+ ion as identified by NMR and electronic spectroscopy. Carbon monoxide release was confirmed with the myoglobin method and by gas chromatographic analysis of the headspace. CO release was not observed when aqueous I was irradiated with blue light (453nm). Changes in the electronic and1 H NMR spectra indicate that I undergoes photoaquation of 4-bzpy to form cis-[Ru(bpy)2 (CO)(H2 O)]2+ . Blue light irradiation of aqueous II released the coordinated 4-bzpy to give the cis-[Ru(bpy)2 (H2 O)(Cl)]2+ ion. When the latter reaction was carried out in the presence of the nucleobase guanine, Ru-guanine adducts were formed, indicating that the metal containing photoproduct may also participate in biologically relevant reactions. The photochemical behavior of I indicates that it can release either CO or 4-bzpy depending on the wavelength chosen, a feature that may have therapeutic application.