Probing the electronic structure of ether functionalised ionic liquids using X-ray photoelectron spectroscopy

Dick, Ejike J.; Fouda, Adam E. A.; Besley, Nicholas A.; Licence, Peter

doi:10.1039/c9cp01297d

Cited by 7 publications

(9 citation statements)

References 58 publications

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“…Indeed, as grafting has only been carried out for 15 min, the SAM is still in the organization process and, therefore, the presence of such residue is not surprising. For the cationic part of the solvent (1-butyl-3- methylimidazolium), three components are present at 286.6, 287.1 and 287.8 eV as evidenced in the literature [28] . For the anionic part (bis(trifluoromethanesulfonyl)imide), a peak at 293.1 eV is present corresponding to CF 3 groups [28] .…”

Section: Resultssupporting

confidence: 52%

Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids

Naidji

Hallez

Taouil

et al. 2021

Ultrasonics Sonochemistry

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Highlights Ionic liquids were used to sonicate a “non vapor” media. In absence of vapor, cavitation is controlled by gas pressure. Cavitation influences orientation and organization of self-assembled monolayers. Chemical adsorption of molecules is highly activated by cavitation. Chemical adsorption of molecules is not dependent on cavitation intensity.

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Section: Resultssupporting

confidence: 52%

Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids

Naidji

Hallez

Taouil

et al. 2021

Ultrasonics Sonochemistry

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“…In the literature, there is a consensus on the existence of bonding between the ether oxygen and ring hydrogens, although there is no agreement on whether this interaction would be site-specific, as this intramolecular interaction would not be strong enough to significantly disrupt the cation–anion interaction. ,,, Here, we show that there is a preferential interaction site with the C(2)–H, and the acetate is free to interact with the other hydrogens on the ring as shown in the dihedral profile scan of the N–C–C– X ( X = O or C), as depicted in Figure .…”

Section: Resultsmentioning

confidence: 63%

“…Interestingly, bidentate coordination becomes preferred for side chains functionalized with alcohol and ether groups. This slight change in the coordination state can be elucidated by the presence of an electronegative atom within the side chain, which makes the neighboring carbon atom electron deficient . This deficiency enhances the site’s propensity to interact with acetate ions, with the effect being more pronounced in the carbon between the oxygens, i.e., for the C 1 OC 1 OC 2 side chain, explaining the increasing in the intensity of the D2 component.…”

Section: Resultsmentioning

confidence: 99%

The Coiling Effect in Ether Ionic Liquids: Exploiting Acetate as a Probe for Transport Properties and Microenvironment Analysis

R. de Moraes,

Paschoal,

Keppeler

et al. 2024

J. Phys. Chem. B

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The inherently high viscosity of ionic liquids (ILs) can limit their potential applications. One approach to address this drawback is to modify the cation side chain with ether groups. Herein, we assessed the structure−property relationship by focusing on acetate (OAc), a strongly coordinating anion, with 1,3-dialkylimidazolium cations with different side chains, including alkyl, ether, and hydroxyl functionalized, as well as their combinations. We evaluated their viscosity, thermal stabilities, and microstructure using Raman and infrared (IR) spectroscopies, allied to density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The viscosity data showed that the ether insertion significantly enhances the fluidity of the ILs, consistent with the coiling effect of the cation chain. Through a combined experimental and theoretical approach, we analyzed how the OAc anion interacts with ether ILs, revealing a characteristic bidentate coordination, particularly in hydroxyl functionalized ILs due to specific hydrogen bonding with the OH group. IR spectroscopy showed subtle shifts in the acidic hydrogens of imidazolium ring C(2)−H and C(4,5)−H, suggesting weaker interactions between OAc and the imidazolium ring in ether-functionalized ILs. Additionally, spatial distribution functions (SDF) and dihedral angle distribution obtained via AIMD confirmed the intramolecular hydrogen bonding due to the coiling effect of the ether side chain.

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“…differences can be understood in terms of the ability of electrons surrounding the atom with the core-hole to react to the creation of that core-hole, akin to the polarizability of the neighboring atoms. Almost all experimental XPS studies of ILs have assumed that the initial-state interpretation holds. − ,− Calculated core binding energies, E B (core,calc. ), for a small number of IL ion pairs in the initial-state approximation (without a core-hole) and the final-state approximation (with a core-hole) , gave reasonable matches to experimental data, and comparisons of E B (core,exp.)…”

Section: Introductionmentioning

confidence: 99%

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

Gousseva,

Towers Tompkins,

Seymour

et al. 2024

J. Phys. Chem. B

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Using a combination of experiments and calculations, we have gained new insights into the nature of anion−cation interactions in ionic liquids (ILs). An X-ray photoelectron spectroscopy (XPS)-derived anion-dependent electrostatic interaction strength scale, determined using XPS core-level binding energies for IL cations, is presented here for 39 different anions, with at least 18 new anions included. Linear correlations of experimental XPS core-level binding energies for IL cations with (a) calculated core binding energies (ab initio molecular dynamics (AIMD) simulations were used to generate high-quality model IL structures followed by single-point density functional theory (DFT) to obtain calculated core binding energies), (b) experimental XPS core-level binding energies for IL anions, and (c) other anion-dependent interaction strength scales led to three main conclusions. First, the effect of different anions on the cation can be related to ground-state interactions. Second, the variations of anion-dependent interactions with the identity of the anion are best rationalized in terms of electrostatic interactions and not occupied valence state/unoccupied valence state interactions or polarizability-driven interactions. Therefore, the XPS-derived anion-dependent interaction strength scale can be explained using a simple electrostatic model based on electrostatic site potentials. Third, anion−probe interactions, irrespective of the identity of the probe, are primarily electrostatic, meaning that our electrostatic interaction strength scale captures some inherent, intrinsic property of anions independent of the probe used to measure the interaction strength scale.

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Probing the electronic structure of ether functionalised ionic liquids using X-ray photoelectron spectroscopy

Abstract: The charge distribution associated with individual components in functionalised ionic liquids (ILs) can be tuned by careful manipulation of the substituent groups incorporated into the ions.

Cited by 7 publications

References 58 publications

Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids

Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids

The Coiling Effect in Ether Ionic Liquids: Exploiting Acetate as a Probe for Transport Properties and Microenvironment Analysis

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

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