Abstract
AbstractThrough photocrystallography at T = 80 K, light‐induced linkage isonitrosyl NO isomers (κO‐bound) are detected and refined in the complex fac‐[RuNO(NO2)2Py2OH]·H2O (Py = pyridine) after irradiation with light in the blue spectral range. The infrared and Raman spectra reveal the downshift of the ν(NO), ν(Ru–NO), and δ(Ru–N–O) vibrations by 120–150 cm–1 upon photoexcitation. Furthermore, the infrared spectrum show a significant downshift of the νas(NO2) and νs(NO2) bands by ca. 10 cm–1 but without any isomerization of the NO2 ligands. Furthermore, the downshifts of the ν(Ru–O–H) and δ(Ru–O–H) vibrational modes show the trans influence of the NO isomer on the OH ligand. The populations of the isonitrosyl isomer determined (66–75 % at λ = 443–445 nm) by all three techniques (X‐ray crystallography, IR and Raman spectroscopy) agree well. Such a high population of the isonitrosyl structure is visible in the photodifference map. The activation parameters Ea = 63.9 ± 1 kJ/mol and k0 = (1.8 ± 0.1) × 1013 s–1 of the reverse transition were determined by differential scanning calorimetry (DSC). The second metastable state (side‐on κ2NO mode) was generated by a two‐step irradiation with blue light followed by irradiation with light in the near‐infrared spectral range (980 nm) and identified through its characteristic NO stretching vibration at $\tilde {\nu}$ = 1592 and 1600 cm–1.
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