Probing the Photoinduced Metal−Nitrosyl Linkage Isomerism of Sodium Nitroprusside in Solution Using Transient Infrared Spectroscopy

We study photoinduced metal−nitrosyl linkage isomerism in sodium nitroprusside (Na2[FeII(CN)5NO]·2H2O, SNP) dissolved in methanol using picosecond transient infrared (IR) spectroscopy. The high sensitivity of this technique allows the simultaneous observation of two known metastable (MS) iron−nitrosyl linkage isomers of SNP, [FeII(CN)5(η1-ON)]2− (MS1) and [FeII(CN)5(η2-NO)]2− (MS2), at room temperature. The transient population of free nitrosyl radicals (NO·) is also measured in the sample solution. These three transient species are detected using their distinct nitrosyl stretching frequencies at 1794 cm−1 (MS1), 1652 cm−1 (MS2), and 1851 cm−1 (NO·). The metastable isomers and NO· are formed on a subpicosecond time scale and have lifetimes greater than 100 ns. A UV (400 nm)−pump power dependence study reveals that MS1 can be formed with one photon, while MS2 requires two photons to be populated at room temperature in solution. Other photodissociation products including cyanide ion, Prussian blue, and [FeI...