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Effect of Bulky Anion around the Dication on the Electronic Structure and Normal Frequencies in 1,3-Bis(3-methylimidazolium-1-yl)propane Bis(trifluoromethanesulfonyl)imide Ionic Liquid.

ABSTRACT: A manifestation of hydrogen bonding between the dication and anions attributed to their relative position of the anions around the cation can influence both the conformational equilibrium and the physical properties of ionic liquids. With this view, we studied the electronic structure and normal frequencies using density functional theory calculations to analyze the hydrogen-bonding interactions in dicationic ionic liquids. The conformers are distinguished based on the hydrogen-bonding sites of the cation and anion. The weak hydrogen bonding between the dication and anions in dication ionic liquids can lead to greater conformational equilibrium compared to the monocation system. Consequences of these interactions for the vibrational spectrum are analyzed to provide an insight into the conformational equilibrium in dicationic ionic liquids at the molecular level.

SUBMITTER: Dhumal NR

PROVIDER: S-EPMC8444328 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Effect of Bulky Anion around the Dication on the Electronic Structure and Normal Frequencies in 1,3-Bis(3-methylimidazolium-1-yl)propane Bis(trifluoromethanesulfonyl)imide Ionic Liquid.

Dhumal Nilesh R NR Seol Kyung K Isaev Dmitry D Helminen Michelle M Williams Brooke B Latortue Sherly S

ACS omega 20210901 36

A manifestation of hydrogen bonding between the dication and anions attributed to their relative position of the anions around the cation can influence both the conformational equilibrium and the physical properties of ionic liquids. With this view, we studied the electronic structure and normal frequencies using density functional theory calculations to analyze the hydrogen-bonding interactions in dicationic ionic liquids. The conformers are distinguished based on the hydrogen-bonding sites of ...[more]

PMID: 34549129

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Project description:In this study, the physicochemical properties and molecular interactions between zirconium-based metal-organic framework (UiO-66) and three different ionic liquids based on bis(trifluoromethanesulfonyl)imide anion (EMIM+, BMIM+ and OMIM+) was performed via a combined experimental and computational approach. The ionic liquid loaded UiO-66 or IL@UiO-66 was synthesized and characterized to understand the host-guest interaction. Density functional theory calculation was performed to analyse the electronic structure of IL@UiO-66 to provide molecular insight on the dominant interactions occurred in the hybrid material. Results showed that all ILs were successfully incorporated into the micropores of UiO-66. The 3D framework was retained even after loaded with ILs as analyzed from XRD pattern. FTIR spectrum reveals that interactions of ILs with UiO-66 influenced by the alkyl chain length of the cation. The anion has a profound affinity with the UiO-66 due to the presence of electronegative atoms. Phase transition study from DSC suggested that the incorporation of ILs has stabilized the framework of UiO-66 by shifting the endothermic peak to a higher state. These findings were further elaborated with DFT calculation. Geometrical optimizations confirmed the structural parameter changes of UiO-66 when loaded with ILs. These was mainly contributed by the non-covalent interactions which was confirmed by the reduced density gradient scattered plot. Another important findings are the strength of hydrogen bonding at the host-guest interface was influenced by the alkyl chain length. The molecular orbital analysis also shows that the size of alkyl chain influence the reactivity of the hybrid material. The present study provides fundamental insights on the molecular interaction of UiO-66 and ILs as a hybrid material, which can open new possibilities for advanced material for metal-organic framework applications in energy storage system, catalysis, gas storage and medicinal chemistry.

Project description:An understanding of the nature of molecular interactions among the ion pairs of 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide [EMI[FSI]] can offer a starting point and significant insight into the more dynamic and multiple interactions within the bulk liquid state. In this context, close inspection of ion pair conformers can offer insight into the effects in bulk [EMI][FSI] liquid. The current work, therefore, gives a detailed analysis of the [EMI][FSI] ion pair conformers through analysis of the interaction energies, stabilization energies, and natural orbital of the ion pair conformers. The structures of the cations, anions, and cation-anion ion pairs of the conformers are optimized systematically by the ωB97X-D method with the DGDZVP basis sets, considering both the empirical dispersion corrections and the presence of a polar solvent, and the most stable geometries are obtained. The [FSI]- anions, unlike [TFSI]- anions, exist at the top position with respect to imidazolium rings. The presence of out-of-plane interactions between the [EMI]+ and [FSI]- ions is in good agreement with the stronger interactions of the [FSI]- anions with alkyl group hydrogens. The presence of out-of-plane conformers could also be related to the interaction of the anion with the π clouds of the [EMI]+ ring. In the [EMI]+ cation, the aromatic ring is π-acidic due to the presence of a positive charge in the N1-C1-N2 ring, which leads to the presence of [FSI]- anion donor [EMI]+ π-acceptor type interactions. The [EMI]+ cation and [FSI]- anions tend to form multiple σ* and π* interactions but reduce the strength of the individual contributions from a potential (linear) maximum. For the ion pair [EMI][FSI], the absolute value of the interaction energies is lower than the normal hydrogen bond energy (50 kJ/mol), which indicates that there is a very weak electrostatic interaction between the [EMI]+ cations and [FSI]- anions. The weaker attraction between the [EMI]+ and [FSI]- ions is suggested to contribute to the larger diffusion coefficients of the ions.

Dataset Information

Effect of Bulky Anion around the Dication on the Electronic Structure and Normal Frequencies in 1,3-Bis(3-methylimidazolium-1-yl)propane Bis(trifluoromethanesulfonyl)imide Ionic Liquid.

Publications

Effect of Bulky Anion around the Dication on the Electronic Structure and Normal Frequencies in 1,3-Bis(3-methylimidazolium-1-yl)propane Bis(trifluoromethanesulfonyl)imide Ionic Liquid.

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