Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light-Induced Linkage NO Isomers in [RuNO(NO2)(2)(pyridine)(2)OH]

Abstract : Through photocrystallography at T = 80 K, light- induced linkage isonitrosyl NO isomers (.O- bound) are detected and refined in the complex fac-[ RuNO( NO2) 2Py2OH] center dot H2O ( Py = pyridine) after irradiation with light in the blue spectral range. The infrared and Raman spectra reveal the downshift of the.( NO),.( Ru- NO), and delta( Ru- N- O) vibrations by 120150 cm- 1 upon photoexcitation. Furthermore, the infrared spectrum show a significant downshift of the (vas)( NO2) and (vs)( NO2) bands by ca. 10 cm- 1 but without any isomerization of the NO2 ligands. Furthermore, the downshifts of the.( RuO- H) and delta( 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. = 443445 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) x 1013 s- 1 of the reverse transition were determined by differential scanning calorimetry ( DSC). The second metastable state ( side- on (KNO)-N-2 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. V = 1592 and 1600 cm- 1.
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European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2015, pp.4905-4913. 〈10.1002/ejic.201500702〉
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Soumis le : vendredi 12 mai 2017 - 12:06:31
Dernière modification le : jeudi 11 janvier 2018 - 06:23:18

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Gennadiy A. Kostin, Alexander O. Borodin, Artem A. Mikhailov, Natalia V. Kuratieva, Boris A. Kolesov, et al.. Photocrystallographic, Spectroscopic, and Calorimetric Analysis of Light-Induced Linkage NO Isomers in [RuNO(NO2)(2)(pyridine)(2)OH]. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2015, pp.4905-4913. 〈10.1002/ejic.201500702〉. 〈hal-01521799〉

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