On the coordination of Zn2+ ion in Tf2N− based ionic liquids: structural and dynamic properties depending on the nature of the organic cation

• Published in: Physical chemistry chemical physics : PCCP 2018-01, Vol.20 (4), p.2662-2675
• Main Authors: Sessa, Francesco, Migliorati, Valentina, Serva, Alessandra, Lapi, Andrea, Aquilanti, Giuliana, Mancini, Giordano, D'Angelo, Paola
• Format: Article
• Language: English
• Subjects: Anions; Cations; Choline; Crystal structure; Crystallography; Dilution; Fine structure; Ionic liquids; Ions; Molecular dynamics; Oxygen atoms; Quantitative analysis; Reliability analysis; Reliability engineering; Simulation; Solvation; Spectrum analysis; Structural reliability; X-rays; Zinc
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c7cp07497b

A synergic approach combining molecular dynamics (MD) simulations and X-ray absorption spectroscopy has been used to investigate diluted solutions of zinc bis(trifluoromethanesulfonyl)imide (Zn(Tf2N)2) in Tf2N− based ionic liquids (ILs) having different organic cations, namely the 1-butyl-3-methylimidazolium ([C4(mim)]+), 1,8-bis(3-methylimidazolium-1-yl)octane ([C8(mim)2]2+), N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium ([Choline]+) and butyltrimethylammonium ([BTMA]+) ions. All of the ILs tend to dissolve the Zn(Tf2N)2 species giving rise to a different structural arrangement around the Zn2+ as compared to that of the salt crystallographic structure. A quantitative analysis of the Zn K-edge extended X-ray absorption fine structure (EXAFS) spectra of the solutions has been carried out based on the microscopic description of the systems derived from the MD simulations. A very good agreement between theoretical and experimental EXAFS signals has been obtained, allowing us to assess the reliability of the MD structural results for all the investigated solutions. The Zn2+ ion has been shown to be coordinated by six oxygen atoms of the Tf2N− anions arranged in an octahedral geometry in all the Tf2N− based ILs, regardless of the organic cation of the IL solvent. However, the nature of the organic cation has a small influence on the overall spatial arrangement of the Tf2N− anions in the Zn2+ first solvation shell: two different Zn–Tf2N complexes are found in solution, a 5-fold one, with one bidentate and four monodentate Tf2N− anions, and a 6-fold one with only monodentate ligands, with the ratio between the two species being slightly dependent on the IL cation. The IL ion three-dimensional arrangements in the different IL solutions were also investigated by carrying out a thorough analysis of the MD simulations, highlighting similarities and differences between imidazolium and ammonium based IL systems.