The investigation of the extraction properties of a series of polyoligodentate β-aminophosphine oxides 1–8 bearing from one to six phosphine oxide groups in a molecule towards Ln(III) and alkaline earth metals ions from neutral media has revealed that, using common diluents, the extraction efficiency increases with an increase of a number of P=O functions in a ligand. The addition of ionic liquid, namely 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([bmim][NTf2]), significantly increasing the extraction efficiency and application of IL concentration of 0.05 M (in 1,2-dichloroethane) providing the maximum recovery of metal ions with Lu/La separation factor reaching up to 91. Hexapodal tris[bis(2-diphenylphosphorylethyl)aminoethyl]amine 8 demonstrates the highest extraction under all conditions applied and the separation factor for U and Eu of this compound exceeded 103. <alternatives> [...] </alternatives>
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