Unusual Hydration Properties of Choline Fluoride-Based Deep Eutectic Solvents.

The hydration properties of the fluoride-based deep eutectic solvent ethalineF [a solution of choline fluoride in ethylene glycol (EG) at a 1:2 molar ratio] are studied and compared to the most common deep eutectic solvent ethaline (the solution of choline chloride in EG at 1:2 molar ratio). The densities of the deep eutectic solvent (DES) based on choline fluoride in EG (ethalineF) and its mixtures with water as cosolvent are measured over the temperature range of 298-323 K. The excess properties, including excess molar volumes, excess partial molar volumes, and viscosity deviations from ideal behavior, are calculated for ethalineF/water and ethaline/water mixtures and compared. The experimental excess molar volumes and viscosity deviations of the studied pseudobinary mixtures are fitted using the Redlich-Kister (R-K) equation. The results of the R-K model successfully reproduced the experimentally calculated values with minimal standard deviations. All excess molar volumes and viscosity deviations had negative values, indicating stronger solvation interactions between the mixture components than between each pure DES or water. The excess partial molar volumes show that water molecules are preferentially solvated by the DES environment. We show that the disruption of the DES interactions (primarily OH...halide interactions) by high mole fractions of water is related to the peak ionic conductivity. The stark differences in hydration behavior between fluoride- and chloride-based ethaline are analyzed and discussed.

Enhanced Dynamics and Charge Transport at the Eutectic Point: A New Paradigm for the Use of Deep Eutectic Solvent Systems.

Deep eutectic solvents (DESs) are a class of versatile solvents with promise for a wide range of applications, from separation processes to electrochemical energy storage technologies. A fundamental understanding of the correlation among the structure, thermodynamics, and dynamics of these materials necessary for targeted rational design for specific applications is still nascent. Here, we employ differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS), and femtosecond transient absorption spectroscopy (fs-TAS) to investigate the correlation among thermodynamics, dynamics, and charge transport in mixtures comprising a wide range of compositions of choline chloride (ChCl) and ethylene glycol (EG). Detailed analyses reveal that (i) the eutectic composition of this prototypical DES occurs in the 15-20 mol % ChCl in the EG range rather than the previously assumed 33 mol %, and (ii) both rotational dynamics and charge transport at the eutectic composition are enhanced in this composition range. These findings highlight the fundamental interplay between thermodynamics and dynamics in determining the properties of DESs that are relevant to many applications.

Redox-Active Eutectic Electrolyte with Viologen and Ferrocene Derivatives for Flow Batteries.

Nonflammable eutectic solvents show great potential to enhance the concentrations of the redox-active materials and the cell voltages for redox flow batteries (RFBs). Herein, we report a promising redox-active eutectic electrolyte (1.5 M total redox species) with viologen and ferrocene derivatives where both of the redox reactions are reversible with a maximum open-circuit voltage of 1.35 V and an energy density of 15.1 Wh L-1, which is relevant to large-scale energy storage. The charge-discharge (from 75 to 25% state of charge) characteristics in a flow cell (0.15 M negolyte and 0.3 M posolyte) showed that it can be cycled with consistent discharge capacity for 12 h (19 cycles), beyond which pressure-driven crossover between the posolyte and negolyte reservoirs leads to capacity decay. This study points to promising new directions toward eutectic electrolyte development for RFBs where we demonstrate increasing the polarity, functionalizing the redox molecules, and separating redox intermediates to prevent undesired side reactions can make improvements in operating cell voltage, energy density, and cyclability.

Solvation Dynamics of Wet Ethaline: Water is the Magic Component.

The past two decades witnessed the development of a new type of solvent system, named deep eutectic solvents, which have become increasingly investigated because they offer new and potentially favorable properties, such as wide tunability in electrochemical, mechanical, and transport properties. Deep eutectic solvent (DES) systems are composed of at least one main solvent and an additional component that is meant to interrupt the original solvent/solvent interactions, thereby introducing lower melting points relative to each individual component. Ethaline (a 1:2 mol % mixture of choline chloride and ethylene glycol) is one of the most promising DES systems. However, it is also known to be very hygroscopic, which is a constant concern because water absorption during the use of ethaline alters its properties. Within this work, we demonstrate that modest amounts of water addition (1-10%) to ethaline are of little concern for practical use and can even lead to performance improvements, such as accelerated relaxation and solvation. In contrast, very small amounts of <1% of water lead to additional slowing of the solvent response. Thus, we suggest that the attempt to dry ethaline below 1% moisture is rather counterproductive if one attempts to achieve effective solvation and charge transport properties from DESs. This study investigates the effect of water content on the diffusional relaxation dynamics of ethaline. A set of independent spectroscopic experiments and computational simulations are aimed to provide insight into the solvent response of the DES system using femtosecond time-resolved absorption spectroscopy (fs-TA), broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR) diffusometry and broadband relaxometry, and molecular dynamics simulations (MDS) on ethaline with 0, 0.1, 1, 10, and 28.5 wt % added water. For dry ethaline, we identify choline chloride as the rate-limiting solvation component in ethaline. However, the role of the solvent components changes gradually as water is added. We provide quantitative solvent relaxation rates using the different presented time-resolved spectroscopic techniques and find remarkable agreement between them. Based on the solvent relaxation rates and combined with MDS, we develop a molecular understanding of the individual solvent components and their interactions in dry and wet ethaline with varying amounts of water content.

Structural Characterization of Thermochromic and Spin Equilibria in Solid-State Ni(detu)4Cl2 (detu = N,N'-Diethylthiourea).

Consecutive thermochromic lattice distortional and spin crossover equilibria in solid-state Ni(detu)4Cl2 (detu = N,N'-diethylthiourea) are investigated by variable-temperature X-ray crystallography (173-333 K), DFT calculations, and differential scanning calorimetry. Thermochromism and anomalous magnetism were reported previously (S. L. Holt, Jr., et al. J. Am. Chem. Soc. 1964, 86, 519-520); the latter was attributed to equilibration of a singlet ground state and a thermally accessible triplet state, but structural data were not obtained. A crystal structure at 173(2) K revealed [Ni(detu)4](2+) centers with distorted planar ligation of nickel(II) to the four sulfur atoms, with an average Ni-S bond length of 2.226(3) Å. The nickel ion was displaced out-of-plane by 0.334 Å toward a proximal apical chloride at a nonbonding distance of 3.134(1) Å. Asymmetry in the trans S-Ni-S angles was coupled to a monoclinic ↔ tetragonal lattice distortion (T(1/2) = 254 ± 11 K), resulting in thermochromism. Spin crossover occurs by tetragonal modulation of nickel(II) with approach of the proximal chloride at higher temperatures (T(1/2) = 383 ± 18 K), which is consistent with a contraction of -0.096(4) Å in the Ni···Cl separation observed at 293 K. A high-spin (S = 1) square-pyramidal [Ni(dmtu)4Cl](+) model (dmtu = N,N'-dimethylthiourea) was optimized by DFT calculations, which estimated limiting equatorial Ni-S bond lengths of 2.45 Å and an apical Ni-Cl bond of 2.43 Å. Electronic spectra of the spin isomers were calculated by TD-DFT methods. Assignment of the FTIR spectrum was assisted by frequency calculations and isotope substitution.