Design and synthesis of pyridinium chiral ionic liquids tethered to a urea functionality

Nine chiral room-temperature ionic liquids (RTILs), which contain a chiral moiety and a urea functionality bonded to a pyridinium ring, have been designed and synthesized. The synthesis of these ionic liquids is concise and practical due to the commercial availability of the starting materials. These novel RTILs were readily prepared from 2-(aminomethyl)pyridine and amino acid ester derived isocyanates. We envision that these new chiral RTILs can serve as effective reaction media as well as chiral catalysts for asymmetric reactions, which are presently being investigated in our laboratory.     

Greener Solvents: Room Temperature Ionic Liquids from Biorenewable Sources

Room temperature ionic liquids (RTILs) have attracted a great deal of interest as environmentally benign (green) solvents for organic synthesis. More recently, RTILs that are chiral, less expensive, or functionalized (protic or Lewis basic) have been developed. In many cases, these new solvents are based on the modification of natural products. This paper is an overview of these new biorenewable RTILs.     

咪唑基离子液体固定分离CO2的研究进展

以咪唑基离子液体为代表,综述了近期普通咪唑基离子液体、功能咪唑基离子液体、支撑咪唑基离子液体和聚合咪唑基离子液体在分离固定CO2方面的研究进展,说明了各类咪唑基离子液体分离固定CO2的可行性及优缺点,并总结了离子液体固定CO2的影响因素和分离机制.     

一类新型二价离子液体的合成及其结构和性质关系的初步研究

设计合成了一类新型的二价离子液体, 并对其结构和性质之间的关系进行探讨.     

Property of ionic liquid in electrophoresis and its application in chiral separation on microchips

The aqueous solution of a kind of room-temperature ionic liquids (RTILs), 1-ethyl-3-methylimidazolium-tetrafluoroborate (1E-3MI-TFB), demonstrated its exclusive electroosmotic property in microchip electrophoresis. It was applied as the working electrolyte for chiral separation in glass microchip electrophoresis. Compared with boric acid buffer, 1E-3MI-TFB aqueous solution exhibited a broader separation window for enantiomers of dipeptides. Then the influences of chiral selector, pH and concentration on efficiency of chiral separation were discussed in detail. The unique mechanism of the generation of EOF was explored in a glass microchannel using 1E-3MI-TFB aqueous solution as working electrolyte. A possible status of 1E-3MI cation in water was suggested at the first time, which facilitated the explanation of EOF and its characteristics in glass microchannel. Additionally, microchip electrophoresis using 1E-3MI-TFB aqueous solution was successfully applied to the chiral separation of complex enantiomers of dipeptides. RTILs aqueous solution, as the electrolyte for the separation of complicated optical isomers, could lead to a revolution in the analytical methods of chiral or conformational analysis for biomolecules.     

Room Temperature Ionic Liquids in Asymmetric Hetero-Ene Type Reactions: Improving Organocatalyst Performance at Lower Temperatures

Room temperature ionic liquids (RTILs) have been widely used as (co)solvents in several catalytic processes modifying, in most of the cases, the catalyst activity and/or the selectivity for the studied reactions. However, there are just a few examples of their use in hydrogen bonding organocatalysis. In this paper, we show the positive effect of a set of imidazole-based ionic liquids ([bmim]BF₄ and [hmim]PF₆) in the enantioselective addition of formaldehyde tert-butylhydrazone to prochiral α-keto esters catalyzed by a sugar-based chiral thiourea. Reactions performed in the presence of low percentages of RTILs led to an increase of the catalyst activity, thereby making possible to work at lower temperatures. Thus, the chiral tert-butyl azomethyl tertiary alcohols could be obtained with moderate to good conversions and higher enantioselectivities for most of the studied substrates when using up to 30 vol% of [hmim]PF₆ as a cosolvent in processes performed in toluene.     

Highly enantioselective alpha-aminoxylation of aldehydes and ketones in ionic liquids

As the first example for the synthesis of optically active alpha-hydroxyaldehydes and alpha-hydroxyketones in ionic liquids, we applied RTILs into L-proline catalyzed direct enantioselective alpha-aminoxylation of both aldehydes and ketones successfully. This protocol features a number of advantages, such as recycling of green solvents and chiral organocatalyst, high yields, excellent enantioselectivities, short reaction times, and broad substrate scope.     

Why are viscosities lower for ionic liquids with -CH2Si(CH3)3 vs -CH2C(CH3)3 substitutions on the imidazolium cations?

We have prepared novel room temperature ionic liquids (RTILs) with trimethylsilylmethyl (TMSiM)-substituted imidazolium cations and compared the properties of these liquids with those for which the TMSiM group is replaced by the analogous neopentyl group. The ionic liquids are prepared with both tetrafluoroborate (BF(4)(-)) and bis(trifluoromethylsulfonyl)imide (NTf(2)(-)) anions paired with the imidazolium cations. At 22 degrees C, the TMSiM-substituted imidazolium ILs have shear viscosities that are reduced by a factor of 1.6 and 7.4 relative to the alkylimidazolium ILs for the NTf(2)(-) and BF(4)(-) anions, respectively. To understand the effect of silicon substitution on the viscosity, the charge densities have been calculated by using density functional theory electronic structure calculations. The ultrafast intermolecular, vibrational, and orientational dynamics of these RTILs have been measured by using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). The intermolecular dynamical spectrum provides an estimate of the strength of interactions between the ions in the RTILs, and provides a qualitative explanation for the observed reduction in viscosity for the silicon-substituted RTILs.     

How ionic are room-temperature ionic liquids? An indicator of the physicochemical properties

Room-temperature ionic liquids (RTILs) are liquids consisting entirely of ions, and their important properties, e.g., negligible vapor pressure, are considered to result from the ionic nature. However, we do not know how ionic the RTILs are. The ionic nature of the RTILs is defined in this study as the molar conductivity ratio (Lambda(imp)/Lambda(NMR)), calculated from the molar conductivity measured by the electrochemical impedance method (Lambda(imp)) and that estimated by use of pulse-field-gradient spin-echo NMR ionic self-diffusion coefficients and the Nernst-Einstein relation (Lambda(NMR)). This ratio is compared with solvatochromic polarity scales: anionic donor ability (Lewis basicity), E(T)(30), hydrogen bond donor acidity (alpha), and dipolarity/polarizability (pi), as well as NMR chemical shifts. The Lambda(imp)/Lambda(NMR) well illustrates the degree of cation-anion aggregation in the RTILs at equilibrium, which can be explained by the effects of anionic donor and cationic acceptor abilities for the RTILs having different anionic and cationic backbone structures with fixed counterparts, and by the inductive and dispersive forces for the various alkyl chain lengths in the cations. As a measure of the electrostatic interaction of the RTILs, the effective ionic concentration (C(eff)), which is a dominant parameter for the electrostatic forces of the RTILs, was introduced as the product of Lambda(imp)/Lambda(NMR) and the molar concentration and was compared with some physical properties, such as reported normal boiling points and distillation rates, glass transition temperature, and viscosity. A decrease in C(eff) of the RTILs is well correlated with the normal boiling point and distillation rate, whereas the liquid-state dynamics is controlled by a subtle balance between the electrostatic and other intermolecular forces.     

Ultrafast dynamics of room temperature ionic liquids after ultraviolet femtosecond excitation

The photochemistry and relaxation dynamics of four room-temperature ionic liquids (RTILs) after ultraviolet (UV) photolysis were investigated by femtosecond pump-probe absorption spectroscopy. A pulse duration-limited rise of the induced absorption in halide-containing RTILs at various probe wavelengths was attributed to the generation of solvated electrons. With continuous irradiation (static conditions), di- and trihalide ion formation became apparent especially below 1000 nm. The formation of trihalide ions was further confirmed by steady-state UV absorption spectroscopy. All RTILs showed a rich photochemistry after UV photolysis leading to the build-up of various long-lived intermediate products as evidenced from the observation that ionic liquids turn yellow upon continuous irradiation. On the other hand, exposing RTILs to the excitation pulse for a short time (rapid-scan method) significantly suppressed the formation of halides. The results suggest that the development of flow-cell systems for highly viscous ionic liquids is urgently needed to quantitatively investigate their ultrafast dynamics.     

A RISM approach to the liquid structure and solvation properties of ionic liquids

We test for the first time the performance of the reference interaction site model (RISM) to predict the liquid structure and solvation of room-temperature ionic liquids (RTILs) represented with different degrees of accuracy. The model gives satisfactory results, proposing itself as a possible method to explore and to describe at a chemically realistic level the solvation shell in ionic liquids, which is believed to play a fundamental role in the static electronic and vibrational properties of these systems.     

Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy

We report on the molecular interactions between room-temperature ionic liquids (RTILs) and Nafion and PDMS membranes, proving that in contact with these polymers RTILs behave like electrolytes rather than solvents.     

Application of Ionic Liquids in Electrochemistry—Recent Advances

In this review, the roles of room temperature ionic liquids (RTILs) and RTIL based solvent systems as proposed alternatives for conventional organic electrolyte solutions are described. Ionic liquids are introduced as well as the relevant properties for their use in electrochemistry (reduction of ohmic losses), such as diffusive molecular motion and ionic conductivity. We have restricted ourselves to provide a survey on the latest, most representative developments and progress made in the use of ionic liquids as electrolytes, in particular achieved by the cyclic voltammetry technique. Thus, the present review comprises literature from 2015 onward covering the different aspects of RTILs, from the knowledge of these media to the use of their properties for electrochemical processes. Out of the scope of this review are heat transfer applications, medical or biological applications, and multiphasic reactions.     

Solvents from biorenewable sources: ionic liquids based on fructose

[reaction: see text] Fructose has been used as the starting material for the preparation of a new class of room-temperature ionic liquids (RTILs). These liquids exhibit tunable solvent properties much like conventional imidazole-based RTILs. They have been applied as recyclable solvents for the Heck reaction of aryl iodides.     

Dipolar solvation dynamics in room temperature ionic liquids: an effective medium calculation using dielectric relaxation data

Solvation dynamics in four imidazolium cation based room temperature ionic liquids (RTIL) have been calculated by using the recently measured dielectric relaxation data [ J. Phys. Chem. B 2008, 112, 4854 ] as an input in a molecular hydrodynamic theory developed earlier for studying solvation energy relaxation in polar solvents. Coumarin 153 (C153), 4-aminophthalimide (4-AP), and trans-4-dimethylamino-4'-cyanostilbene (DCS) have been used as probe molecules for this purpose. The medium response to a laser-excited probe molecule in an ionic liquid is approximated by that in an effective dipolar medium. The calculated decays of the solvent response function for these RTILs have been found to be biphasic and the decay time constants agree well with the available experimental and computer simulation results. Also, no probe dependence has been found for the average solvation times in these ionic liquids. In addition, dipolar solvation dynamics have been predicted for two other RTILs for which experimental results are not available yet. These predictions should be tested against experiments and/or simulation studies.     

离子液体在CO_2捕集中的应用进展

离子液体具有蒸汽压极低、热稳定性好、热容低和可以根据目标需求进行设计等特性,能克服传统CO2捕集工艺的诸多不足,因而成为目前CO2捕集溶剂的研究热点。本文主要综述了普通离子液体、功能化离子液体、支撑型离子液体膜、聚合型离子液体和离子液体复配溶液在CO2捕集方面的应用研究进展,评述了各种方法的优势和缺点,并在此基础上提出...     

Nanostructural organization and anion effects on the temperature dependence of the optical Kerr effect spectra of ionic liquids

The intermolecular spectra of three imidazolium ionic liquids were studied as a function of temperature by the use of optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids comprise the 1,3-pentylmethylimidazolium cation ([C(5)mim]+), and the anions, bromide (Br-), hexafluorophosphate (PF(6)-), and bis(trifluoromethanesulfonyl)imide (NTf(2)-). Whereas the optical Kerr effect (OKE) spectrum of [C(5)mim][NTf(2)] is temperature-dependent, the OKE spectra of [C(5)mim]Br and [C(5)mim][PF6] are temperature-independent. These results are surprising in light of the fact that the bulk densities of these room temperature ionic liquids (RTILs) are temperature-dependent. The temperature independence of the OKE spectra and the temperature dependence of the bulk density in [C(5)mim]Br and [C(5)mim][PF(6)] suggest that there are inhomogeneities in the densities of these liquids. The existence of density inhomogeneities is consistent with recent molecular dynamics simulations that show RTILs to be nanostructurally organized with nonpolar regions arising from clustering of the alkyl chains and ionic networks arising from charge ordering of the anions and imidazolium rings of the cations. Differences in the temperature dependences of the OKE spectra are rationalized on the basis of the degree of charge ordering in the polar regions of the RTILs.     

Transport properties of room-temperature ionic liquids from classical molecular dynamics

Room-temperature ionic liquids (RTILs) have attracted much attention in the scientific community in the past decade due their novel and highly customizable properties. Nonetheless, their high viscosities pose serious limitations to the use of RTILs in practical applications. To elucidate some of the physical aspects behind transport properties of RTILs, extensive classical molecular dynamics calculations are reported. Here, in particular, bulk viscosities and ionic conductivities of butyl-methyl-imidazole based RTILs are presented over a wide range of temperatures. The dependence of the properties of the liquids on simulation parameters, e.g., system-size effects or the choice of the interaction potential, is analyzed in detail.     

室温离子液体的分子动力学模拟

室温离子液体作为一种新型的反应介质正在受到人们的关注,近十年来成为了化学领域的研究热点。随着人们对离子液体结构与性质研究的不断深入和计算方法的快速发展,分子模拟已是研究离子液体的结构和性质的有力工具。本文介绍了分子动力学(molecular dynamics,MD)的基本原理,分子力场的种类,以及离子液体分子动力学模拟一般采用的AMBER、OPLS和CHARMM三种力场的构建形式。综述了近年来纯组分离子液体、混合组分离子液体分子动力学模拟方法研究取得的成果和最新进展,并分析了主要存在的问题。展望了离子液体分子动力学模拟的研究方向和前景,同时还提出了包含极化作用和静电远程作用的离子液体分子动力学模拟研究的基本思路。     

The double role of ionic liquids in organic electrosynthesis: Precursors of N-heterocyclic carbenes and green solvents. Henry reaction

N-heterocyclic carbenes, electrogenerated by cathodic reduction of imidazolium-based room temperature ionic liquids (RTILs), are stable bases able to catalyze the Henry reaction. Accordingly, the electrosynthesis of β-nitroalcohols has been achieved, under mild conditions and in high yields, by stirring nitromethane and aldehydes in previously electrolyzed RTILs. RTILs have been used as green solvents as well as precursors of N-heterocyclic carbenes.