Abstract. The synthesis, lanthanide complexation and solvent extraction of actinide(III) and lanthanide(III) radiotracers from nitric acid solutions by a phenanthroline-derived quadridentate bis-2 triazine ligand is described. The ligand separates Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity and fast extraction kinetics compared to its 2,2'-bipyridine counterpart. Structures of the 1:2 bis complexes of the ligand with Eu(III) and Yb(III) were elucidated by X-ray crystallography and force field calculations, respectively. The Eu(III) bis-complex is the first 1:2 bis-complex of a quadridentate bis-triazine ligand to be characterized by crystallography. The faster rates of extraction were verified by kinetics measurements using the rotating membrane cell technique in several diluents. The improved kinetics of metal ion extraction are related to the higher surface activity of the ligand at the phase interface. The improvement in the ligands properties on replacing the bipyridine unit with a phenanthroline unit far exceeds what was anticipated based on ligand design alone.

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We report here experimental evidence for the formation in the solid state of a new binuclear Fe (III) 2(mu-OMe) 2(HL) 4 complex (H 2L is 2-salicyloylhydrazono-1,3-dithiolane). The isostructural Mn (III) 2(mu-OMe) 2(HL) 4 complex has provided the strongest ferromagnetic interaction value (J approximately 20 cm (-1)) between Mn (III) ions to date. The new iron binuclear compound presented in this study shows antiferromagnetic intramolecular coupling, which agrees with the theoretical study that we previously proposed. During our synthetic work, we also observed an unexpected spontaneous reduction of the new Fe (III)(HL) 2Cl,S complex to the new Fe (II)(H 2L) 2Cl 2 high-spin mononuclear complex. This process has been checked by cyclo-voltammetry as well as pseudosteady voltammetry.