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Structural and Thermodynamic Properties of Transition Metal Ions in Room Temperature Ionic Liquids
Full text linkRoom temperature ionic liquids (RTILs) are salts made by an organic cation and an organic or inorganic anion, which are at the liquid state at 25 °C. RTILs have attracted much attention as new sustainable solvents owing to some unique properties they usually possess, such as a practically negligible vapor pressure, non-flammability, high thermal stability, wide electrochemical windows, good solvation ability and supposed low toxicity. These features make RTILs good candidates for the substitution of classical organic solvents in many technological applications. For these reasons, they are currently studied as new media for chemical separations, electrodepositions, electrolytes for batteries and supercapacitors, catalysis and pharmaceutical research.
Several of these applications also involve the presence of metal ions as solvated species in RTILs. In this field, structural and thermodynamic data about single-ion solvation are fundamental quantities that need to be known to improve new technologies. However, this fundamental knowledge still lacks for many metal species in several ionic liquids. The aim of this thesis is to obtain a complete description of metal ions solvation in RTILs both from a structural and thermodynamic point of view.
Molecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) experiments have been performed to study solutions of metal ions of industrial, environmental and economic interest such as Zn2+, Co2+, Ag+ in widely used RTILs like those based on the [Tf2N]- (bis(trifluoromethylsulfonyl)imide) and [BF4]- (tetrafluoroborate) anions within the [Cnmim]+ (1-alkyl-3-methylimidazolium) cation.
MD simulations have been carried out on Zn2+ in [Cnmim][Tf2N] (n = 2, 4) and [C4mim][BF4]. The obtained thermodynamic data are in good agreement with literature experimental values and indicate the goodness of the employed protocol. The calculated Gibbs free energies of transfer (ΔGtrans) from water to the [Cnmim][Tf2N] RTILs suggest that Zn2+ is more favorably solvated in aqueous solution than in this class of ionic liquids, while the opposite is found for [C4mim][BF4]. The obtained single-ion solvation enthalpies and entropies provided an interpretation of the different contributions to the calculated free energies. In addition, XAS experimental results allowed to understand the coordination of Zn2+ in water-saturated [C4mim][Tf2N], representing the real-operating condition in a liquid-liquid extraction.
A similar picture has been obtained for Co2+ in [C4mim][Tf2N]. MD calculated ΔGtrans showed that the metal ion is still more favorably solvated in water than in the RTIL because of an unfavorable entropic contribution. XAS experiments and data-fitting allowed to obtain Co2+ coordination in dry [C4mim][Tf2N]. The metal resulted to be bound by six monodentate anions forming the [Co(Tf2N)6]4- octahedral species. In addition, water is found to preferentially coordinate the metal when present at high concentrations in the RTIL, as provided by UV-Vis data.
As regards the study about Ag+ in RTILs, a totally different picture with respect to Zn2+ and Co2+ has been obtained. MD results showed that this ion is more favorably solvated both in [C4mim][Tf2N] and [C4mim][BF4] with respect to water, and this encourages the employment of these RTILs as extracting phase for this metal. Ag+ resulted coordinated by four or five RTILs anions, depending on the employed interaction potential. However, when considering the transfer of Ag+ from water to the RTILs, great care must be taken because of a possible change in the coordination number. Indeed, preliminary XAS data suggest a linear coordination for this metal ion in aqueous solution, differently from the tetrahedral model that is usually accepted and reproduced by the current classical potentials. Ab initio MD simulations with the Car-Parrinello method seemed to confirm this observation
Solvation of Zn 2+ ion in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids: A molecular dynamics and X-ray absorption study
No full textOn the coordination chemistry of the lanthanum(III) nitrate salt in EAN/MeOH mixtures
Full text linkA 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
Direct Observation of Contact Ion-Pair Formation in La(3+) Methanol Solution
Full text link[Image: see text] 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(3))(3) solutions in water and methanol, with the aim of elucidating the still elusive coordination of the La(3+) 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(3))(3) salt is fully dissociated and the La(3+) 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(3+) 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(3))(3) solutions in the two solvents, showing the distinct presence of the nitrate counterions in the La(3+) 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
In-Depth XANES and EXAFS Characterization of the Ag+ Ion Coordination in Dimethyl Sulfoxide Solution
No full textX-ray absorption near-edge structure (XANES) spectroscopy has been used, in conjunction with extended X-ray absorption fine structure (EXAFS), to determine the coordination structure of the Ag+ ion in a dimethyl sulfoxide (DMSO) solution. From the EXAFS data analysis, the Ag-O first shell distance in DMSO was found to be 2.31(3) & Aring;, with 4.1(5) oxygen atoms surrounding the Ag+ ion, in fair agreement with previous results. This technique did not allow us to determine the geometry of the 4-fold coordination complex and a quantitative analysis of the XANES region was carried out to shed light on this issue. The XANES data analysis confirmed the presence of a four-coordinated complex, unambiguously showing that a regular tetrahedral [Ag(DMSO)(4)](+) complex is formed when silver triflate is dissolved in DMSO solution
Hydrophobicity as the key to understanding the nanostructural behavior of eutectic mixtures upon apolar cosolvent addition
Full text linkThe influence of the addition of the apolar n-hexane (HEX) cosolvent on the structural arrangement of eutectic mixtures with different degrees of hydrophobicity, namely butylated hydroxytoluene (BHT), L-menthol (MEN), thymol (TYM), and choline chloride (ChCl), has been studied with a combined approach using small- and wide-angle X-ray scattering and molecular dynamics simulations. The cosolvent introduction has a similar impact on the molecular scale-length aggregation in BHT:MEN:HEX, TYM:MEN:HEX, and ChCl:TYM:HEX mixtures at different 1:3:H, 1:2:H, and 1:7:H molar ratios, specifically a dramatic perturbation of the main interactions present in the pure eutectics where hydrogen-bonds dominate. On larger scale-lengths, HEX addition results in a homogeneous electron-density distribution in the BHT:MEN:HEX and TYM:MEN:HEX mixtures due to a high affinity of the cosolvent for the BHT, MEN, and TYM components. Conversely, the presence of the more hydrophilic ChCl compound in the ChCl:TYM 1:7 system is the driving force for the segregation mechanism of this component which causes the formation of nano-scale inhomogeneities at high HEX concentrations, before macroscopic phase separation. The different degree of hydrophobicity is therefore key to understanding the nanostructural behavior of these eutectics in the presence of an apolar cosolvent. These findings have important implications for the employment of deep eutectic solvent mixtures, as the formation of pseudo-phase aggregates can help explaining the macroscopic behavior of these alternative media in applications like extraction procedures
Solubilization and coordination of the HgCl2 molecule in water, methanol, acetone, and acetonitrile: an X-ray absorption investigation
No full textX-ray absorption spectroscopy (XAS) has been employed to carry out structural characterization of the local environment around mercury after the dissolution of the HgCl2 molecule. A combined EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) data analysis has been performed on the Hg L3-edge absorption spectra recorded on 0.1 M HgCl2 solutions in water, methanol (MeOH), acetone and acetonitrile. The Hg-Cl distance determined by EXAFS (2.29(2)-2.31(2) Å) is always comparable to that found in the HgCl2 crystal (2.31(2) Å), demonstrating that the HgCl2 molecule dissolves in these solvents without dissociating. A small sensitivity of EXAFS to the solvent molecules interacting with HgCl2 has been detected and indicates a high degree of configurational disorder associated with this contribution. XANES data analysis, which is less affected by the disorder, was therefore carried out for the first time on these systems to shed light into the still elusive structural arrangement of the solvent molecules around HgCl2. The obtained results show that, in aqueous and MeOH solutions, the XANES data are compatible with three solvent molecules arranged around the HgCl2 unit to form a trigonal bipyramidal structure. The determination of the three-body Cl-Hg-Cl distribution shows a certain degree of uncertainty around the average 180° bond angle value, suggesting that the HgCl2 molecule probably vibrates in the solution around a linear configuration
Coordination of the Co2+ and Ni2+ Ions in Tf2N Based Ionic Liquids: A Combined Xray Absorption and Molecular Dynamics Study
Full text linkMolecular dynamics (MD) simulations and X-ray absorption spectroscopy (XAS) have been combined to study the coordination of the Co2+ and Ni2+ ions in ionic liquids (ILs) based on the bis(trifluoromethylsulfonyl)imide ([Tf2N]-) anion and having different organic cations, namely, 1-butyl-3-methylimidazolium ([C4mim]+), 1,8-bis(3-methylimidazolium-1-yl)octane ([C8(mim)2]2+), N,N,N-trimethyl-N-(2-hydroxyethyl)ammonium ([choline]+), and butyltrimethylammonium ([BTMA]+). Co and Ni K-edge XAS data have been collected on 0.1 mol L-1 Co(Tf2N)2 and Ni(Tf2N)2 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(Tf2N)2 and Ni(Tf2N)2 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 Co2+ and Ni2+ ions are surrounded by a first solvation shell formed by six [Tf2N]- 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 [Tf2N]- anions, so that stable octahedral complexes of the type [M(Tf2N)6]4- (M = Co, Ni) have been observed in all the investigated ILs
Mercury Monohalides as Ligands in Transition Metal Complexes
Full text linkThe main categories of transition metal–mercury heterometallic compounds are briefly summarized. The attention is focused on complexes and clusters where the {Hg-Y} fragment, where Y represents a halide atom, interacts with transition metals. Most of the structurally characterized derivatives are organometallic compounds where the transition metals belong to the Groups 6, 8, 9 and 10. More than one {Hg-Y} group can be present in the same compound, interacting with the same or with different transition metals. The main synthetic strategies are discussed, and structural data of representative compounds are reported. According to the isolobality with hydrogen, {Hg-Y} can form from one to three M-{Hg-Y} bonds, but further interactions can be present, such as mercurophilic and Hg···halide contacts. The formal oxidation state of mercury is sometimes ambiguous and thus {Hg-Y} can be considered as a Lewis acid or base on varying the transition metal fragment. Density functional theory calculations on selected Group 6 and Group 9 model compounds are provided in order to shed light on this aspect
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