Abstract
A thorough structural characterization of the La(NO(3))(3) salt dissolved into several mixtures of ethyl ammonium nitrate (EAN) and methanol (MeOH) with EAN molar fraction χ(EAN) ranging from 0 to 1 has been carried out by combining molecular dynamics (MD) and X-ray absorption spectroscopy (XAS). The XAS and MD results show that changes take place in the La(3+) first solvation shell when moving from pure MeOH to pure EAN. With increasing the ionic liquid content of the mixture, the La(3+) first-shell complex progressively loses MeOH molecules to accommodate more and more nitrate anions. Except in pure EAN, the La(3+) ion is always able to coordinate both MeOH and nitrate anions, with a ratio between the two ligands that changes continuously in the entire concentration range. When moving from pure MeOH to pure EAN, the La(3+) first solvation shell passes from a 10-fold bicapped square antiprism geometry where all the nitrate anions act only as monodentate ligands to a 12-coordinated icosahedral structure in pure EAN where the nitrate anions bind the La(3+) cation both in mono- and bidentate modes. The La(3+) solvation structure formed in the MeOH/EAN mixtures shows a great adaptability to changes in the composition, allowing the system to reach the ideal compromise among all of the different interactions that take place into it.