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Report No.

XAFS and spectroscopic characterization for the structure and electronic structure of Ce-DMDPhPDA complexes in methanol

Yaita, Tsuyoshi; Shiwaku, Hideaki   ; Suzuki, Shinichi; Okamoto, Yoshihiro  ; Shimada, Asako*; Assefa, Z.*; Haire, R. G.*

The structural parameter and the electronic structure of the complex between cerium and N,N'-dimethyl-N,N'-diphenylpyridine-2,6-carboxyamide(DMDPhPDA) was investigated by XAFS, photo luminescence and excitation spectra. The DMDPhPDA is one of the promising ligands for separation of trivalent actinides from lanthanides. The Ce-K XAFS spectra were measured at BL11XU of SPring-8. The bond distances between the carbonyl oxygens and cerium, and between the pyridyl nitrogen and cerium are 253pm and 264pm, respectively. The bond angle of the plane consisting of the two carbonyl oxygens and nitrogen with cerium was about 180 degree. This complex was a yellow color unique for the DMDPhPDA-lanthanide complexes. The photo absorption peak for the complex was extremely broad, and the peak position was at a higher wavenumber as compared with those for the other lanthanide complexes. The peak in the highest wavenumber of this band may be attributed to the transition between f and d orbitals, which are greatly influenced by the ligand field of the DMDPhPDA. The XANES spectrum of the cerium complex clearly showed that cerium was trivalent.



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