Structure of 1-Ethyl-3-Methylimidazolium Chloroaluminates: Neutron Diffraction Measurements and <i>ab initio</i> Calculations

Takahashi, Satoshi; Suzuya, Kentaro; Kohara, Shinji; Koura, Nobuyuki; Curtiss, Larry A.; Saboungi, Marie‐Louise

doi:10.1524/zpch.1999.209.part_2.209

Cited by 70 publications

(65 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…83 Over the past ten years, great ] -made based on neutron scattering data and its direct analysis or indirect interpretation through modelling. However, for ionic liquids, apart from one study by Takahashi et al 84 where data was collected on [C 2 mim]Cl-AlCl 3 ionic liquids and was interpreted through simulation, the focus of neutron scattering experiments has been on ionic liquids with metal-free anions, 85,86 and particularly on materials with static anion configurations rather than the dynamic equilibria commonly found in the halometallate systems. Neutron scattering provides information about the total structure within liquids (or glasses) and when combined with techniques such as XAS that inform on local environments, and computational modelling should be able to provide a detailed picture about how the changes in metallate anion speciation that occur with changing mole fraction affect the bulk structural properties of ionic liquids.…”

Section: Neutron Scatteringmentioning

confidence: 99%

Halometallate ionic liquids – revisited

Estager¹,

2014

View full text Add to dashboard Cite

Ionic liquids with chlorometallate anions may not have been the first ionic liquids, however, it was their development that lead to the recognition that ionic liquids are a distinct, and useful, class of (functional) materials. While much of the phenomenal interest and attention over the past two decades has focussed on 'air and water stable' ionic liquids, research and application of chlorometallate systems has continued unabated albeit largely out of the main spotlight. The defining characteristic of chlorometallates is the presence of complex anionic equilibria, which depend both on the type and on the concentration of metal present, and leads directly to their characteristic and individual properties. Here, we review the experimental techniques that can be applied to study and characterise the anion speciation in these ionic liquids and, using recent examples, illustrate how their applications base is evolving beyond traditional applications in Lewis acidic catalysis and electrochemistry through to uses as soft and component materials, in the ionothermal synthesis of semiconductors, gas storage systems and key components in the development of biomass processing.

show abstract

Section: Neutron Scatteringmentioning

confidence: 99%

Halometallate ionic liquids – revisited

Estager¹,

2014

View full text Add to dashboard Cite

show abstract

“…Early studies on ionic liquids are limited to the chloroaluminate melts. [42][43][44][45][46][47] A number of studies treat isolated imidazolium cations but have primarily been directed toward producing parameters for use in force fields. [36,38,39,48] More recently, imidazolium-based ionic liquids have been examined in which the anion has been one or more of a halide, [BF 4 À .…”

Section: =Cmentioning

confidence: 99%

Characterising the Electronic Structure of Ionic Liquids: An Examination of the 1‐Butyl‐3‐Methylimidazolium Chloride Ion Pair

Hunt

Kirchner

Welton

2006

Chemistry A European J

439

389

View full text Add to dashboard Cite

In this paper we analyse the electronic properties of gas-phase 1-butyl-3-methylimidazolium Cl ion pairs, [C(4)C(1)im]Cl, in order to deepen our understanding of ionic liquids in general. Examination of charge densities, natural bond orbitals (NBO), and delocalised molecular orbitals computed at the B3LYP and MP2/6-31(++)G(d,p) levels have enabled us to explain a number of experimental phenomena: the relative acidity of different sites on the imidazolium ring, variations in hydrogen-bond donor and acceptor abilities, the apparent contradiction of the hydrogen-bond-donor parameters for different types of solute, the low probability of finding a Cl(-) anion at the rear of the imidazolium ring and the expansion of the imidazolium ring in the presence of a strong hydrogen-bond acceptor. The unreactive but coordinating environment and large electrochemical window have also been accounted for, as has the strong electron-donating character of the carbon atoms to the rear of the ring in associated imidazolylidenes. The electronic structure of the [C(4)C(1)im](+) cation is best described by a C(4)==C(5) double bond at the rear, and a delocalised three-centre 4 e(-) component across the front (N(1)-C(2)-N(3)) of the imidazolium ring; delocalisation between these regions is also significant. Hydrogen-bond formation is driven by Coulombic stabilisation, which compensates for an associated destabilisation of the electronic part of the system. Interactions are dominated by a large positive charge at C(2) and the build up of pi-electron density above and below the ring, particularly that associated with the double bond between C(4) and C(5). The NBO partial charges have been computed and compared with those used in a number of classical simulations.

show abstract

“…A number of experimental (NMR spectroscopy [176][177][178][179], vibrational spectroscopy [160,173,174,[180][181][182] and neutron diffraction [148,161,183]) studies have also been employed for investigating structures of ionic liquids, except those mentioned above. Results of another interesting characterization method, electronspray ionization mass spectroscopy, have recently revealed that an ionic liquid can form aggregates and their size depends on the solvent used and the ionic liquid concentration [184,185].…”

Section: Related Studiesmentioning

confidence: 99%

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

Matsumoto

Hagiwara

2007

Journal of Fluorine Chemistry

View full text Add to dashboard Cite

An overview of recent structural studies on alkylimidazolium-based salts containing fluoroanions is presented. Alkylimidazolium cations have been most extensively used for syntheses of ionic liquids (room temperature molten salts) because they usually exhibit low melting points, low viscosities and high conductivities. This review mainly focuses on structures of alkylimidazolium-based salts combined with a fluorocomplex anion ((FH) n F À , BF 4 À , PF 6 À , AsF 6 À , SbF 6 À , NbF 6 À , TaF 6 À ), N(SO 2 CF 3 ) 2 À (TFSI À ) and OSO 2 CF 3 À . The first part describes crystal structures of these salts and the second part describes computational, spectroscopic and diffraction studies on their liquid structures. Related studies on ionic liquids of non-alkylimidazolium cation and non-fluoroanion are also briefly summarized. #

show abstract

Structure of 1-Ethyl-3-Methylimidazolium Chloroaluminates: Neutron Diffraction Measurements and ab initio Calculations

Cited by 70 publications

References 17 publications

Halometallate ionic liquids – revisited

Halometallate ionic liquids – revisited

Characterising the Electronic Structure of Ionic Liquids: An Examination of the 1‐Butyl‐3‐Methylimidazolium Chloride Ion Pair

Structural characteristics of alkylimidazolium-based salts containing fluoroanions

Contact Info

Product

Resources

About