Dynamical Heterogeneities in Ionic Liquids as Revealed from Deuteron NMR | Sciact - CRIS-system of Boreskov Institute of Catalysis

Dynamical Heterogeneities in Ionic Liquids as Revealed from Deuteron NMR Full article

Journal

Chemical Communications
ISSN: 1359-7345 , E-ISSN: 1364-548X

Output data

Year: 2018, Volume: 54, Number: 25, Pages: 3098-3101 Pages count : 4 DOI: 10.1039/c7cc09440j

Tags

QUADRUPOLE COUPLING-CONSTANTS; INTERACTION ENERGIES; DISPERSION FORCES; HYDROGEN-BONDS; RELAXATION; SOLVENTS; MACROMOLECULES; MIXTURES; FUTURE; MEDIA

Authors

Khudozhitkov Alexander E. ^1,2 , Stange Peter ³ , Bonsa Anne-Marie ³ , Overbeck Viviane ³ , Appelhagen Andreas ^3,4 , Stepanov Alexander G. ^1,2 , Kolokolov Daniil I. ^1,2 , Paschek Dietmar ³ , Ludwig Ralf ^3,4

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	Universität Rostock, Institut für Chemie, Abteilung für Physikalische Chemie, Dr-Lorenz-Weg 2, 18059 Rostock, Germany
4	Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany

Funding (2)

1	Federal Agency for Scientific Organizations	0303-2016-0003
2	German Research Foundation	LU 506 14-1

The heterogeneity in dynamics has important consequences for understanding the viscosity, diffusion, ionic mobility, and the rates of chemical reactions in technology relevant systems such as polymers, metallic glasses, aqueous solutions, and inorganic materials. Herein, we study the spatial and dynamic heterogeneities in ionic liquids by means of solid state NMR spectroscopy. In the 2H spectra of the protic ionic liquid [TEA][OTf] we observe anisotropic and isotropic signals at the same time. The spectra measured below the melting temperature at 306 K could be simulated by a superposition of the solid and liquid line shapes, which provided the transition enthalpies between the rigid and mobile fractions. Consequently, we measured the spin–lattice relaxation times T1 for the anisotropic and the isotropic signals for the temperature range between 203 and 436 K. Both dispersion curves could be fitted to models including rotational correlation times, activation barriers and rate constants. This approach allowed determining the rotational correlation times for the N–D molecular vector of the [TEA]+ cation in differently mobile environments. The mobility is only slightly different, as indicated by small differences in activation energies for these processes. The NMR correlation times for the highly mobile phase are linearly related to measured viscosities, which supports the applicability of the Stokes–Einstein–Debye relation.

Khudozhitkov A.E. , Stange P. , Bonsa A-M. , Overbeck V. , Appelhagen A. , Stepanov A.G. , Kolokolov D.I. , Paschek D. , Ludwig R.
Dynamical Heterogeneities in Ionic Liquids as Revealed from Deuteron NMR
Chemical Communications. 2018. V.54. N25. P.3098-3101. DOI: 10.1039/c7cc09440j WOS Scopus РИНЦ ANCAN PMID OpenAlex

Submitted:	Dec 12, 2017
Accepted:	Feb 12, 2018
Published online:	Feb 12, 2018
Published print:	Mar 28, 2018

Web of science:	WOS:000428845500004
Scopus:	2-s2.0-85044285515
Elibrary:	35502183
Chemical Abstracts:	2018:260336
Chemical Abstracts (print):	168:313783
PMID:	29464242
OpenAlex:	W2787042986

DB	Citing
Web of science	21
Scopus	21
Elibrary	17
OpenAlex	44