Relationship Between Structure and Coordination Strength of N and N,O-Hybrid Donor Ligands with Trivalent Lanthanides |
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| Authors: | Masahiko Nakase Tohru Kobayashi Hideaki Shiwaku Shinichi Suzuki Travis S. Grimes Bruce J. Mincher |
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| Affiliation: | 1. Aqueous Separation and Radiochemistry Department, Idaho National Laboratory, Idaho Falls, Idaho, USA;2. Actinide Chemistry Group, Japan Atomic Energy Agency, Hyogo, Japanmasahiko.nakase@inl.gov;4. Actinide Chemistry Group, Japan Atomic Energy Agency, Hyogo, Japan |
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| Abstract: | ABSTRACTTo effectively separate lanthanides (Ln(III)) from actinides (An(III)), symmetrical 2,2′-bipyridyl (Bpy), 1,10-phenanthroline (Phen), and unsymmetrical N-methyl-N-tolyl-1,10-phenanthroline-2-carboxamide (MeTol-PTA) were investigated. According to the crystal structures and EXAFS experiments, the decreasing ionic radius from light to heavy Ln led to decreases in the Ln–N (Bpy) and Ln–N (Phen) distances, while log β simply increased due to the electrostatic interaction and the order of Ln–O (MeTol-PTA) < Ln–N (Bpy, Phen) < Ln–N (MeTol-PTA) was obtained. This indicated that the bulky phenanthroline moiety of MeTol-PTA may not allow N (MeTol-PTA) to come close to Ln. Consequently, the log β of MeTol-PTA exhibited a local maximum (around Nd). |
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| Keywords: | NO-hybrid donor lanthanides single crystal EXAFS stability constants |
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