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Ionic liquid extraction of metal(II, III) complexes with macrocyclic and chelating ligands

Okamura, Hiroyuki  

This paper summarizes the author's doctoral thesis on analytical chemistry. In this study, the ionic liquid (IL) extraction of various metal(II, III) complexes with macrocyclic and anionic chelating ligands has been investigated to clarify the solvent effect of ILs and to demonstrate the specificity and superiority of the IL extraction systems over conventional ones. The evaluation of the extraction equilibrium of Eu(III) with 2-thenoyltrifluoroacetone (Htta) in 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C$$_{n}$$mim][Tf$$_{2}$$N]) and time-resolved laser-induced fluorescence spectroscopy revealed the specific solute-solvent interactions between Eu(tta)$$_{3}$$ and [C$$_{n}$$mim][Tf$$_{2}$$N]. The IL synergistic extraction with Htta and ${it cis}$-dicyclohexano-18-crown-6 was developed. The extractability of lighter lanthanides(III) was remarkably enhanced by a synergistic effect of crown ethers. A macrocyclic ligand (H$$_{2}$$$$beta$$DA18C6) composed of diaza-18-crown-6 and two 4-acyl-5-pyrazolones was synthesized for the extraction of Sr(II). The extraction performance of H$$_{2}$$$$beta$$DA18C6 was significantly enhanced only in [C$$_{n}$$mim][Tf$$_{2}$$N] by the intramolecular cooperative effect.

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