Photoinduced electron transfer between the cationic complexes Ru(NH3)5pz2+ and trans-RuCl([15]aneN4)NO2+ mediated by phosphate ion:: Visible light generation of nitric oxide for biological targets

The photochemical behavior of the tetraazamacrocyclic complex trans-RuCl([15]ane)(NO)(2+) (RuNO2+) in a 10 mM phosphate buffer solution, pH 7.4, and in the presence of Ru(NH3)(5)pz(2+) (Rupz(2+)) is reported. Irradiation (436 nm) of an aqueous solution containing both cationic complexes as PF6- salts labilizes NO from RuNO2+ with a quantum yield (phi(NO)) dependent on the concentration of Rupz(2+) with a maximum value of phi(NO) (1.03(11) x 10(-3) einstein mol(-1)) found for a solution with equimolar concentrations (5 x 10(-5) M) of the two complexes in phosphate buffer solution. The quantitative behavior of this system suggests that the two cations undergo preassociation such that photoexcitation of the visible absorbing Rupz(2+) is followed by electron or energy transfer to RuNO2+, which does not absorb appreciably at the excitation wavelength, and this leads to NO release from the reduced nitrosyl complex. Notably, the NO release was not seen in the absence of phosphate buffer; thus, it appears that phosphate ions mediate NO generation, perhaps by facilitating formation of a supramolecular complex between the two ruthenium cations. Reexamination of the cyclic voltammetry of Rupz(2+) showed that the electrochemical behavior of this species is also affected by the presence of the phosphate buffer.