Direct Observation of Contact Ion-Pair Formation in La Methanol Solution.

An approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) has been used to carry out a comparative study about the solvation properties of dilute La(NO) solutions in water and methanol, with the aim of elucidating the still elusive coordination of the La ion in the latter medium. The comparison between these two systems enlightened a different behavior of the nitrate counterions in the two environments: while in water the La(NO) salt is fully dissociated and the La ion is coordinated by water molecules only, the nitrate anions are able to enter the metal first solvation shell to form inner-sphere complexes in methanol solution. The speciation of the formed complexes showed that the 10-fold coordination is preferential in methanol solution, where the nitrate anions coordinate the La cations in a monodentate fashion and the methanol molecules complete the solvation shell to form an overall bicapped square antiprism geometry. This is at variance with the aqueous solution where a more balanced situation is observed between the 9- and 10-fold coordination. An experimental confirmation of the MD results was obtained by La K-edge XAS measurements carried out on 0.1 M La(NO) solutions in the two solvents, showing the distinct presence of the nitrate counterions in the La ion first solvation sphere of the methanol solution. The analysis of the extended X-ray absorption fine structure (EXAFS) part of the absorption spectrum collected on the methanol solution was carried out starting from the MD results and confirmed the structural arrangement observed by the simulations.