Phase behavior of ionic liquids 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides with halogenated benzenes

Siporska, Agnieszka; Szydłowski, Jerzy

doi:10.1016/j.jct.2015.04.012

Cited by 9 publications

(2 citation statements)

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“…Tetra- n -butylammonium picrate and 1-tridecaneol system was reported to have UCST at around 342 K . To get deep understanding, liquid–liquid equilibrium of the [NTf 2 ] − anion based imidazolium ILs with arenes, , haloalkanes and hydrocarbon have been extensively studied and were found to be good solvents for polymers with UCST behavior. , For mixtures of [C n Quin][NTf 2 ] ( n = 4, 6, or 8) with benzene, alkylbenzene, or thiophene, the eutectic systems with mutual immiscibility in the liquid phase with very high UCSTs were observed. − For the binary systems of [C 6 Quin][NTf 2 ] with benzene and alkylbenzenes, eutectic diagrams with immiscibility gaps in the liquid IL phase (beginning from 0.13 to 0.28 mole fraction) with very high UCST were observed. For mixtures of [C 8 Quin][NTf 2 ] with benzene and alkylbenzenes, an immiscibility gap in the liquid phase was detected for low mole fraction of the IL.…”

Section: Thermomorphic Systems Based On Ionic Liquids (Ils)mentioning

confidence: 99%

Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic Applications

et al. 2017

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Temperature-responsive ionic liquids (ILs), their fundanmental behaviors, and catalytic applications were introduced, especially the concepts of upper critical solution temperature (UCST) and lower critical solution temperature (LCST). It is described that, during a catalytic reaction, they form a homogeneous mixture with the reactants and products at reaction temperature but separate from them afterward at ambient conditions. It is shown that this behavior offers an effective alternative approach to overcome gas/liquid-solid interface mass transfer limitations in many catalytic transformations. It should be noted that IL-based thermomorphic systems are rarely elaborated until now, especially in the field of catalytic applications. The aim of this article is to provide a comprehensive review about thermomorphic mixtures of an IL with HO and/or organic compounds. Special focus is laid on their temperature dependence concerning UCST and LCST behavior, including systems with conventional ILs, metal-containing ILs, polymerized ILs, as well as the thermomorphic behavior induced via host-guest complexation. A wide range of applications using thermoregulated IL systems in chemical catalytic reactions as well as enzymatic catalysis were also demonstrated in detail. The conclusion is drawn that, due to their highly attractive behavior, thermoregulated ILs have already and will find more applications, not only in catalysis but also in other areas.

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Section: Thermomorphic Systems Based On Ionic Liquids (Ils)mentioning

confidence: 99%

Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic Applications

et al. 2017

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“…The most common of these are structures where one or more hydrogens are replaced by halogens (C 6 H 6-n X n ; X F, Cl, Br, I; n = 1-6). [1][2][3][4][5][6][7][8][9] In our group, we have recently studied the interaction between singly-substituted halobenzenes (with halogens up to At) and one or two water molecules, in the context of locating possible halogen bonding between the halogen and the water oxygen. [10] Conversely, benzene structures where a carbon is replaced by a halogen have received much less attention so far.…”

Section: Introductionmentioning

confidence: 99%

Halogen bonding with the halogenabenzene bird structure, halobenzene, and halocyclopentadiene

Cates

Mourik

2019

J Comput Chem

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The ability of the “bird‐like” halogenabenzene molecule, referred to as X‐bird (XCl to At), to form halogen‐bonded complexes with the nucleophiles H2O and NH3 was investigated using double‐hybrid density functional theory and the aug‐cc‐pVTZ/aug‐cc‐pVTZ‐PP basis set. The structures and interaction energies were compared with 5‐halocyclopenta‐1,3‐diene (halocyclopentadiene; an isomer of halogenabenzene) and halobenzene, also complexed with H2O and NH3. The unusual structure of the X‐bird, with the halogen bonded to two carbon atoms, results in two distinct σ‐holes, roughly at the extension of the C‐X bonds. Based on the behavior of the interaction energy (which increases for heavier halogens) and van der Waals (vdW) ratio (which decreases for heavier halogens), it is concluded that the X‐bird forms proper halogen bonds with H2O and NH3. The interaction energies are larger than those of the halogen‐bonded complexes involving halobenzene and halocyclopentadiene, presumably due to the presence of a secondary interaction. © 2019 Wiley Periodicals, Inc.

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Pseudo Jahn–Teller origin tracking for symmetry breaking in halogenabenzene: How can a bird fly?

Wang

Liu

Zheng

2018

Int J of Quantum Chemistry

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The cyclic iodabenzene molecule (CH) 5 I was first introduced and characterized as planar configuration and zwitterionic valence structure by Glukhovtsev in 1991. Recently, it caused researchers' great interest due to the theoretical discovery of a stable bird-like structure by Hoffmann et al. in 2017 which has similar electronic structure and charge distribution as wellknown Meisenheimer complex C 6 H − 7 . Inspired by this, we continue to tell the halogenabenzene story by revealing the origin of the bird-like structure and understanding how the electronic behavior affects the geometrical symmetry for a molecule. By combining the Pseudo Jahn-Teller effect (PJTE) theory with the ab initio calculations for halogenabenzenes (CH) 5 X (X = F, Cl, Br, I) and C 6 H − 7 , it is illustrated that the vibronic coupling of 1 A 1 ground state and 1 B 1 excited states with C 2v planar structure along the out-of-plane b 1 distortion triggers the symmetry breaking of planar configuration to form a preferred bird-like structure. This interpretation can be also applied to explain their different stabilization energies by analyzing numerically the energy gaps of coupled electronic states and PJTE vibronic coupling parameters. Taking use of the PJTE formulation above, we also tracked the origin of restoring to be planar for (CH) 5 X 2+ cation, as well as their isoelectronic species (CH) 5 O + and (CH) 5 N, and suggests an effective strategy to stabilize the planar configuration for halogenabenzenes. K E Y W O R D S excited state, halogenabenzene, pseudo Jahn-Teller effect, symmetry breaking, vibronic coupling 1 | INTRODUCTIONWhen referring to halogen-substituted benzene compounds, most of attention has been paid to the cases that hydrogen atoms in different positions of benzene are substituted for halogen atoms, such as C 6 H 5 X [1][2][3][4] and C 6 H 4 X 2 or C 6 X 6 [2-7] (X = F, Cl, Br, I). In contrast, the systems in which the carbon atom is replaced by halogen atom have been rarely reported. The cyclic (CH) 5 I molecule, called iodabenzene, was firstly introduced by Glukhovtsev in 1991 and found to show a planar configuration with 8π electron system based on the semiempirical AM1 and MNDO calculations. [8] More recently, Hoffmann and his coworkers performed more accurate DFT and MP2 calculations on iodabenzene and obtained a stable bird-like minimum structure, which is expected optimistically to be detected and isolated in experiment. [9] It was also described that iodabenzene and its analogues (CH) 5 X (X = F, Cl, Br) have the similar geometric configuration and zwitterionic valence electronic structure to the famous Meisenheimer complexes. [10,11] Besides the neutral halogenabenzene molecules, the cation (CH) 5 X 2+ (X = F, Cl, Br, I), as well as their iso-valence electronic pyrylium cation (CH) 5 O + and pyridine (CH) 5 N, also attracted great interest in literatures. [12][13][14][15] As very common chemical reagents, (CH) 5 O + and (CH) 5 N are applied extensively in the field of organic chemistry. The (CH) 5 O + is used ...

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Phase behavior of ionic liquids 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides with halogenated benzenes

Cited by 9 publications

References 14 publications

Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic Applications

Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic Applications

Halogen bonding with the halogenabenzene bird structure, halobenzene, and halocyclopentadiene

Pseudo Jahn–Teller origin tracking for symmetry breaking in halogenabenzene: How can a bird fly?

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