Coordination of the Co and Ni Ions in TfN Based Ionic Liquids: A Combined X-ray Absorption and Molecular Dynamics Study.

Molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) have been combined to study the coordination of the Co and Ni ions in ionic liquids (ILs) based on the bis(trifluoromethylsulfonyl)imide ([TfN]) anion and having different organic cations, namely, 1-butyl-3-methylimidazolium ([Cmim]), 1,8-bis(3-methylimidazolium-1-yl)octane ([C(mim)]), ,,-trimethyl--(2-hydroxyethyl)ammonium ([choline]), and butyltrimethylammonium ([BTMA]). Co and Ni K-edge XAS data have been collected on 0.1 mol L Co(TfN) and Ni(TfN) solutions and on the metallic salts. MD simulations have been carried out to obtain structural information on the metal ion coordination. The analysis of the extended X-ray absorption fine structure (EXAFS) spectra of the solutions has been carried out based on the atomistic description provided by MD, and the studied ILs have been found to be able to dissolve both the Co(TfN) and Ni(TfN) salts giving rise to a different structural arrangement around the metal ions as compared to the solid state. The combined EXAFS and MD results showed that the Co and Ni ions are surrounded by a first solvation shell formed by six [TfN] anions, each coordinating in a monodentate fashion by means of the oxygen atoms. The nature of the IL organic cation has little or no influence on the overall spatial arrangement of the [TfN] anions, so that stable octahedral complexes of the type [M(TfN)] (M = Co, Ni) have been observed in all the investigated ILs.