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Title: Understanding the ionic liquid [NC4111][NTf2] from individual building blocks: an IR-spectroscopic study

Abstract

This study explores the interactions underlying the IR spectra of the ionic liquid [NC4111][NTf2] and its deuterated isotopomer [d9-NC4111][NTf2] by first isolating the spectra of charged ionic building blocks using mass-selective CIVP spectroscopy and then following the evolution of these bands upon sequential assembly of the ionic constituents. The spectra of the (1,1) and (2,2) neutral ion pairs are recorded using superfluid helium droplets as well as a solid neon matrix, while those of the larger charged aggregates are again obtained with CIVP. In general, the cluster spectra are similar to that of the bulk, with the (2,2) system displaying the closest resemblance. Analysis of the polarization-dependent band intensities of the neutral ion pairs in liquid droplets as a function of external electric field yields dipole moments of the neutral aggregates. This information allows a coarse assessment of the packing structure of the neutral pairs to be antiparallel at 0.37 K, in contrast to the parallel arrangement found for the assembly of small, high-dipole neutral molecules with large rotational constants (e.g., HCN). The role of an extra anion or cation attached to both the (1,1) and the (2,2) ion pairs to form the charged clusters is discussed in the contextmore » of an additional remote, more unfavorable binding site intrinsic to the nature of the charged IL clusters and as such not anticipated in the bulk phase. Whereas for the anion itself only the lowest energy trans conformer was observed, the higher clusters showed an additional population of the cis conformer. Finally, the interactions are found to be consistent with a minimal role of hydrogen bonding.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [2];  [1];  [1];  [3]
  1. Ruhr-Univ. Bochum, Bochum (Germany)
  2. Yale Univ., New Haven, CT (United States)
  3. Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr (Germany)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1741041
Grant/Contract Number:  
FG02-06ER15800
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 17; Journal Issue: 13; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Clusters; Ionic Liquids; Infrared Spectroscopy; Mass Spectrometry

Citation Formats

Hanke, Kenny, Kaufmann, Matin, Schwaab, Gerhard, Havenith, Martina, Wolke, Conrad T., Gorlova, Olga, Johnson, Mark A., Kar, Bishnu Prasad, Sander, Wolfram, and Sanchez-Garcia, Elsa. Understanding the ionic liquid [NC4111][NTf2] from individual building blocks: an IR-spectroscopic study. United States: N. p., 2015. Web. doi:10.1039/c5cp00116a.
Hanke, Kenny, Kaufmann, Matin, Schwaab, Gerhard, Havenith, Martina, Wolke, Conrad T., Gorlova, Olga, Johnson, Mark A., Kar, Bishnu Prasad, Sander, Wolfram, & Sanchez-Garcia, Elsa. Understanding the ionic liquid [NC4111][NTf2] from individual building blocks: an IR-spectroscopic study. United States. https://doi.org/10.1039/c5cp00116a
Hanke, Kenny, Kaufmann, Matin, Schwaab, Gerhard, Havenith, Martina, Wolke, Conrad T., Gorlova, Olga, Johnson, Mark A., Kar, Bishnu Prasad, Sander, Wolfram, and Sanchez-Garcia, Elsa. Thu . "Understanding the ionic liquid [NC4111][NTf2] from individual building blocks: an IR-spectroscopic study". United States. https://doi.org/10.1039/c5cp00116a. https://www.osti.gov/servlets/purl/1741041.
@article{osti_1741041,
title = {Understanding the ionic liquid [NC4111][NTf2] from individual building blocks: an IR-spectroscopic study},
author = {Hanke, Kenny and Kaufmann, Matin and Schwaab, Gerhard and Havenith, Martina and Wolke, Conrad T. and Gorlova, Olga and Johnson, Mark A. and Kar, Bishnu Prasad and Sander, Wolfram and Sanchez-Garcia, Elsa},
abstractNote = {This study explores the interactions underlying the IR spectra of the ionic liquid [NC4111][NTf2] and its deuterated isotopomer [d9-NC4111][NTf2] by first isolating the spectra of charged ionic building blocks using mass-selective CIVP spectroscopy and then following the evolution of these bands upon sequential assembly of the ionic constituents. The spectra of the (1,1) and (2,2) neutral ion pairs are recorded using superfluid helium droplets as well as a solid neon matrix, while those of the larger charged aggregates are again obtained with CIVP. In general, the cluster spectra are similar to that of the bulk, with the (2,2) system displaying the closest resemblance. Analysis of the polarization-dependent band intensities of the neutral ion pairs in liquid droplets as a function of external electric field yields dipole moments of the neutral aggregates. This information allows a coarse assessment of the packing structure of the neutral pairs to be antiparallel at 0.37 K, in contrast to the parallel arrangement found for the assembly of small, high-dipole neutral molecules with large rotational constants (e.g., HCN). The role of an extra anion or cation attached to both the (1,1) and the (2,2) ion pairs to form the charged clusters is discussed in the context of an additional remote, more unfavorable binding site intrinsic to the nature of the charged IL clusters and as such not anticipated in the bulk phase. Whereas for the anion itself only the lowest energy trans conformer was observed, the higher clusters showed an additional population of the cis conformer. Finally, the interactions are found to be consistent with a minimal role of hydrogen bonding.},
doi = {10.1039/c5cp00116a},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 13,
volume = 17,
place = {United States},
year = {Thu Feb 12 00:00:00 EST 2015},
month = {Thu Feb 12 00:00:00 EST 2015}
}

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