We report a theoretical study on the liquid−liquid interfacial behavior of the species involved in the extraction of Cs+ by a calix[4]arene-crown6 ionophore (L):  the free Cs+ Pic- and Cs+ Cl- salts, the LCs+ and LCs+ Pic- complexes, and uncomplexed L. Based on molecular dynamics simulations, we calculated the free energies changes for migration from the interface into the aqueous and the organic phases, respectively. For free L and for the LCs+ complex, with or without Pic- counterion, an energy minimum is found close to the interface, on the chloroform side, showing that these species behave as surfactants. This contrasts with the uncomplexed Cs+, which diffuses spontaneously from the interface to water and displays no energy minimum. A remarkable counterion effect is found with Pic- which displays a high affinity for the interface, while Cl- prefers the bulk aqueous phase. The questions of ion extraction by ionophores, counterions, concentration and synergistic effects in assisted cation transfer through the liquid−liquid interface between immiscible liquids are discussed from the interfacial point of view.

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We report an ab initio quantum mechanical study on the interaction of M(n)()(+) cations (M(n)()(+) = La(3+), Eu(3+), Yb(3+), Sr(2+), and Na(+)) with model ligands L for lanthanide or actinide cations: several substituted amides, pyridines, and the phosphoryl-containing OPPh(3) ligand. The interaction energies DeltaE follow trends expected from the cation hardness and ligand basicity or softness in the amide series (primary < secondary-cis < secondary-trans < tertiary) as well as in the pyridine series (para-NO(2) < H < Me < NMe(2)). Among all ligands studied, OPPh(3) is clearly the best, while the (best) tertiary amide binds lanthanides slightly less than the (best) pyridine-NMe(2) ligand. In the lanthanide 1:1 complexes, the energy differences DeltaDeltaE as a function of M(3+) (about 40 kcal/mol for all ligands) are less than DeltaDeltaE in the pyridine series (up to about 90 kcal/mol) where marked polarization effects are found. The conclusions are validated by a number of methodological investigations. In addition to optimal binding features, we also investigate the directionality of ion coordination to the ligands and the effect of counterions and stoichiometry on the structural, electronic and energetic features of the complexes. The results are discussed in the context of modeling complexes of lanthanide and actinide cations and compared to those obtained with analogous Na(+) and Sr(2+) complexes.