Fabián Vaca Chávez

CO2 in 1-Butyl-3-methylimidazolium Acetate. 2. NMR Investigation of Chemical Reactions

The solvation of CO(2) in 1-butyl-3-methylimidazolium acetate (Bmim Ac) has been investigated by (1)H, (13)C, and (15)N NMR spectroscopy at low CO(2) molar fraction (mf) (x(CO(2)) ca. 0.27) corresponding to the reactive regime described in part 1 of this study. It is shown that a carboxylation reaction occurs between CO(2) and Bmim Ac, leading to the formation of a non-negligible amount (~16%) of 1-butyl-3-methylimidazolium-2-carboxylate. It is also found that acetic acid molecules are produced during this reaction and tend to form with elapsed time stable cyclic dimers existing in pure acid. A further series of experiments has been dedicated to characterize the influence of water traces on the carboxylation reaction. It is found that water, even at high ratio (0.15 mf), does not hamper the formation of the carboxylate species but lead to the formation of byproduct involving CO(2). The evolution with temperature of the resonance lines associated with the products of the reactions confirms that they have a different origin. The main byproduct has been assigned to bicarbonate. All these results confirm the existence of a reactive regime in the CO(2)-Bmim Ac system but different from that reported in the literature on the formation of a reversible molecular complex possibly accompanied by a minor chemical reaction. Finally, the reactive scheme interpreting the carboxylation reaction and the formation of acetic acid proposed in the literature is discussed. We found that the triggering of the carboxylation reaction is necessarily connected with the introduction of carbon dioxide in the IL. We argue that a more refined scheme is still needed to understand in details the different steps of the chemical reaction in the dense phase.

Charge Templates in Aromatic Plus Ionic Liquid Systems Revisited: NMR Experiments and Molecular Dynamics Simulations

The mutual solubilities of [C2C1im][Ntf2] ionic liquid and aromatic molecules (benzene and its fluorinated derivatives) can be correlated to the dipolar and quadrupolar moments of the latter molecules. This fact can be interpreted as a consequence of the charge-induced structuration of the IL ions around the aromatic molecules. In this paper we demonstrate that we can follow the above-mentioned structural changes in the mixtures using different NMR-based techniques, namely 1D (1)H and (13)C NMR and 2D (1)H-(1)H NOESY NMR spectroscopy. These have been complemented by more detailed structural analyses of the different (IL plus aromatic solute) mixtures using MD simulations. Such systematic studies included eight systems, namely mixtures of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid with benzene, fluorobenzene, 1,2-difluorobenzene, 1,4-difluorobenzene, 1,3,5-trifluorobenzene, 1,2,4,5-tetrafluorobenzene, penta-fluorobenzene, and hexafluorobenzene.

1)H NMR Relaxation Study of a Magnetic Ionic Liquid as a Potential Contrast Agent.

A proton nuclear magnetic relaxation dispersion (1)H NMRD study of the molecular dynamics in mixtures of magnetic ionic liquid [P66614][FeCl4] with [P66614][Cl] ionic liquid and mixtures of [P66614][FeCl4] with dimethyl sulfoxide (DMSO) is presented. The proton spin-lattice relaxation rate, R1, was measured in the frequency range of 8 kHz-300 MHz. The viscosity of the binary mixtures was measured as a function of an applied magnetic field, B, in the range of 0-2 T. In the case of DMSO/[P66614][FeCl4] the viscosity was found to be independent from the magnetic field, while in the case of the [P66614][Cl]/[P66614][FeCl4] system viscosity decreased with the increase of the magnetic field strength. The spin-lattice relaxation results were analyzed for all systems taking into account the relaxation mechanisms associated with the molecular motions with correlation times in a range between 10(-11) and 10(-7)s, usually observed by NMRD, and the paramagnetic relaxation contributions associated with the presence of the magnetic ions in the systems. In the case of the DMSO/[P66614][FeCl4] system the R1 dispersion shows the relaxation enhancement due to the presence of the magnetic ions, similar to that reported for contrast agents. For the [P66614][Cl]/[P66614][FeCl4] system, the R1 dispersion presents a much larger paramagnetic relaxation contribution, in comparison with that observed for the DMSO/[P66614][FeCl4] mixtures but different from that reported for other magnetic ionic liquid system. In the [P66614][Cl]/[P66614][FeCl4] system the relaxation enhancement associated with the paramagnetic ions is clearly not proportional to the concentration of magnetic ions, in contrast with what is observed for the DMSO/[P66614][FeCl4] system.

Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

NMR spectroscopy ((1)H, (13)C, (15)N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH3COS(-)), CO2, OCS, and trithiocarbonate (CS3 (2-)). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro](+) cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS2-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO2-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS2 reacts with the acetate anion leading to the formation of CH3COS(-), CO2, and OCS. After these reactions have proceeded the nascent CO2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO2) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO2-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO2, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS2 is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2).

Dynamics of Discotic Fluoroalkylated Triphenylene Molecules Studied by Proton NMR Relaxometry

The Larmor frequency and temperature dependence of the proton nuclear magnetic resonance (NMR) spin-lattice relaxation time was measured in the isotropic and columnar phases of both chain-end fluorinated triphenylene disk-like and fully hydrogenated molecules. In the columnar phase, the results are interpreted in terms of the collective motions, due to the deformations of the columns, and individual molecular translational self-diffusion displacements and rotations/reorientacions. In the isotropic phase, local molecular motions and order fluctuations as a pretransitional effect were considered. The activation energies of the molecular motions of the partially fluorinated molecule were found to be higher than those corresponding to the hydrocarbon homologue. Our findings show a clear difference in the relaxation dispersion between the two liquid crystals homologues. In particular it is observed that the columnar undulations have a much stronger contribution to the relaxation rate in the low frequency regime in the case of the fully hydrogenated triphenylene. The effect of fluorination of the pheripheral chain enhances the columnar mesophases stability.

NMR molecular dynamics study of chromonic liquid crystals Edicol Sunset Yellow doped with salts

We investigate the effect of monoatomic salts on the molecular dynamics in the nematic and isotropic phases formed by the chromonic liquid crystal Edicol Sunset Yellow. The study was carried out using proton nuclear magnetic resonance relaxometry. To analyse the effect of incorporation of additional sodium chloride or lithium chloride on the solutions’ molecular dynamics, the spin‐lattice relaxation time was measured for Larmor frequencies between 10kHz and 100MHz. In the nematic phase, the presence of additional sodium or lithium ions seems to contribute to an increase of the rotations/reorientations correlation times in comparison with the mixture without extra ions. The collective motions detected by proton NMR relaxometry are associated with collective fluctuations of molecules within the stacks in the nematic phase and with order parameter fluctuations in the isotropic phase. Copyright

Proton NMR relaxation study of molecular dynamics of chromonic liquid crystal Edicol Sunset Yellow

Proton nuclear magnetic resonance (1H NMR) relaxometry, over about five decades in Larmor frequency, and pulsed field gradient NMR were used to study the molecular dynamics in the chromonic nematic and isotropic phases of stacked molecules of the binary mixture composed by Edicol Sunset Yellow (ESY) and deuterated water. Our results evidence that in both phases collective motions are responsible for the spin-lattice relaxation dispersion in the Larmor frequency range below 1 MHz. In the nematic phase, the collective motion are attributed to columnar undulations within the stacked molecules, while, in the isotropic phase, the results are explained by local order fluctuations due to the formation of the stacks. The high frequency dispersion was explained by individual molecular motions like rotations around and perpendicular to the stack axis, and also self-diffusion.