Nickel(II) Complexation with Nitrate in Dry ZC4mim][Tf2N] Ionic Liquid: A Spectroscopic, Microcalorimetric, and Molecular Dynamics Study
| Autor: | Marilena Tolazzi, Sylvia Georg, Clotilde Gaillard, Sara Gràcia Lanas, Lola Sarrasin, Isabelle Billard, Maria Boltoeva, Andrea Melchior |
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| Přispěvatelé: | Institut de Physique Nucléaire de Lyon (IPNL), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département Recherches Subatomiques (DRS-IPHC), Institut Pluridisciplinaire Hubert Curien (IPHC), Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de Physique Nucléaire et de Physique des Particules du CNRS (IN2P3)-Centre National de la Recherche Scientifique (CNRS) |
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Extended X-ray absorption fine structure
medicine.diagnostic_test Inorganic chemistry chemistry.chemical_element Isothermal titration calorimetry 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology C4mim 01 natural sciences 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Inorganic Chemistry chemistry.chemical_compound Nickel chemistry Spectrophotometry Ionic liquid medicine Physical and Theoretical Chemistry Absorption (chemistry) 0210 nano-technology Spectroscopy |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, 2016, 55, pp.3498-3507. ⟨10.1021/acs.inorgchem.5b02937⟩ |
| ISSN: | 0020-1669 1520-510X |
| Popis: | The complex formation of nitrate ions with nickel(II) in dry [C4mim][Tf2N] ionic liquid (IL) was investigated by means of UV-visible spectrophotometry, isothermal titration calorimetry (ITC), extended X-ray absorption fine structure spectroscopy (EXAFS), and molecular dynamics (MD) simulations. EXAFS spectroscopy and MD simulations show that the solvated Ni(II) cation is initially coordinated by the oxygens of the [Tf2N](-) anion of IL, which can behave either as mono- or bidentate. Spectroscopic and thermodynamic data show that Ni(II) is able to form up to three stable mononuclear complexes with nitrate in this solvent. The stability constants for Ni(NO3)j complexes (j = 1-3) calculated from spectrophotometry and ITC experiments decrease in the order log K1log K2log K3. The formation of the first two species is enthalpy-driven, while the third species is entropy-stabilized. The UV-vis spectra of solutions containing different nitrate/Ni(II) ratios show that the metal ion retains the six-coordinate geometry. Furthermore, the EXAFS evidences that nitrate is always bidentate. Molecular dynamics simulations show that the [Tf2N](-) anions bind Ni(II) through the sulfonyl oxygen atoms and can coordinate either as monodentate or chelate. The analysis of the MD data shows that introduction of nitrates in the first coordination sphere of the metal ion results in remarkable structural rearrangement of the ionic liquid. |
| Databáze: | OpenAIRE |
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