Evolution of the La(III) ion coordination sphere in ethylammonium nitrate solution upon water addition

A thorough structural study of La(NO3)3 salt solutions in mixtures of the ethylammonium nitrate (EAN) ionic liquid (IL) and water with EAN molar fraction (X EAN) ranging from 0 to 1 has been carried out by means of X-ray absorption spectroscopy (XAS) measurements at the La K-edge and molecular dynamics (MD) simulations. Both the XAS and MD outcomes agree in finding that the composition of the La3+ ion first solvation shell undergoes steadily changes when moving from pure water to pure EAN. Upon increasing of the IL concentration, the La3+ solvation complexes progressively lose water molecules to accommodate more and more nitrate anions, and the ratio between the two ligands continuously changes across the explored composition range. The nitrate ligands coordinate the metal ion only in a monodentate fashion for the lower EAN contents, while the percentage of bidentate nitrates becomes more and more predominant as the EAN concentration increases. When moving from pure water to pure EAN, the La3+ ion coordination passes from a 9-fold tricapped trigonal prismatic geometry to a 12-fold icosahedral one, while a 10-fold coordination with bicapped square antiprism geometry is the dominant species for the mixed compositions. The remarkable flexibility of this solvation complex in accommodating a variable amount of water molecules and nitrate ligands at dependence of the system composition is key for its predominance in all the EAN/water mixtures.