On the Coordination Chemistry of the lanthanum(III) Nitrate Salt in EAN/MeOH Mixtures

• Published in: Inorganic chemistry Vol. 60; no. 14; pp. 10674 - 10685
• Main Authors: Migliorati, Valentina, Gibiino, Alice, Lapi, Andrea, Busato, Matteo, D’Angelo, Paola
• Format: Journal Article
• Language: English
• Published: American Chemical Society 19-07-2021
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.1c01375

A thorough structural characterization of the La­(NO3)3 salt dissolved into several mixtures of ethyl ammonium nitrate (EAN) and methanol (MeOH) with EAN molar fraction χEAN 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 La3+ first solvation shell when moving from pure MeOH to pure EAN. With increasing the ionic liquid content of the mixture, the La3+ first-shell complex progressively loses MeOH molecules to accommodate more and more nitrate anions. Except in pure EAN, the La3+ 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 La3+ 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 La3+ cation both in mono- and bidentate modes. The La3+ 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.