Photolysis of the pentacyanonitrosylferrate (II) ion in sodium nitroprusside (SNP) solutions involves a competition between photosubstitution and photo-oxidation reactions, where the nitrosyl and cyanide ligands can be released as free nitric oxide (NO) or NO+ and free CN- or CN radical. We have irradiated aqueous SNP solutions at several narrow wavelength ranges in the UV/Vis region (314–576 nm), with the aim of investigating the photolability of the CN and NO ligands. Kinetics of photolysis were used to characterize the photosensitivity of SNP solutions in the range 314–576 nm. Spectral changes in the UV/Vis and IR regions upon irradiation and assays for the detection of free CN- and NO, provided additional evidences for the absence of photoprocesses leading to the release of CN- with λirr > 480 nm. In this condition, the main photoproducts were found to be the [FeIII(CN)5(H2O)]2- ion and NO, formed in a intramolecular photo-oxidative process. Irradiation with unfiltered UV/Vis light and with λirr < 480 nm, lead to the release of both CN- and NO and to a mixture of ferrocyanide and ferricyanide products. These results confirm that the exposure of SNP solutions to UV/Vis light below λirr = 480 nm can lead to cyanide poisoning and further support that above this wavelength limit, a selective NO release from SNP can be achieved, with possible implications for its biochemical action.
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