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Lanthanides complexation properties of O, N-hetero donor ligand PTA

Kobayashi, Toru; Suzuki, Shinichi; Shiwaku, Hideaki; Yaita, Tsuyoshi

Development of extractant, which can efficiently separate actinides, is of increasing importance because it concerns establishment and simplification of separation techniques in nuclear fuel cycle and decontamination of radioactive wastes. In this study, the complexation properties of N-alkyl-N-phenyl-1,10-phenanthroline-2-carboxamide (PTA) with trivalent lanthanides (Ln$$^{3+}$$) were investigated based on structural analysis by using X-ray crystallography and extended X-ray absorption fine structure (EXAFS) methods. As a result, it is revealed that two PTA molecules coordinate with Ln$$^{3+}$$ as tridentate ligand via two nitrogen in phenanthroline moiety and one oxygen in amide moiety in both crystal and solution states. The slight difference in coordination bond distances are observed between Eu$$^{3+}$$ and Nd$$^{3+}$$ complexes, this difference corresponds to the difference in ionic radius between Nd$$^{3+}$$ and Eu$$^{3+}$$. This result indicates slight difference in ionic radii of Ln$$^{3+}$$ hardly affects coordination properties of PTA.

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