Electron Paramagnetic Resonance (EPR) and optical spectra of uranium(V) species were observed in both processes of photo- and electrolytic reduction of UO
2(NO
3)
2-2tributylphosphate (TBP) in 80%TBP-n-dodecane solution. The formation of U(V) species was detected by an optical spectrum (
max : 770, 970 and 1, 420 nm). EPR signal with the value of g-factor 2.3 and a linewidth of approximately 1, 100 Gs was observed during the electrolytic reduction. On the other hand, during the photoreduction the signal with the value of g-factor 1.94 was observed and there was found a superhyperfine structure with the intensity ratio of 1 : 2 : 1, that is caused by the superhyperfine coupling with nuclear spin, I=1/2, of the strongly coordinated 31P to the central uranium through oxygen atom. The superhyperfine coupling constant was estimated to be 27 Gs. Moreover, the signal with the value of g-factor 2.00 due to an organic radical was observed. The residue after the thermo-gravimetric analysis of UO
2(NO
3)
2-2TBP was identified as α-UP
2O
7 by the powder X-ray diffraction analysis, indicating the strong coordination of TBP to the central uranium atom.
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