The Influence of Deuterium Isotope Effects on Structural Rearrangements, Ensemble Equilibria, and Hydrogen Bonding in Protic Ionic Liquids | Sciact - CRIS-system of Boreskov Institute of Catalysis

The Influence of Deuterium Isotope Effects on Structural Rearrangements, Ensemble Equilibria, and Hydrogen Bonding in Protic Ionic Liquids Full article

Journal

ChemPhysChem
ISSN: 1439-4235 , E-ISSN: 1439-7641

Output data

Year: 2022, Volume: 23, Number: 23, Article number : e202200557, Pages count : 6 DOI: 10.1002/cphc.202200557, 10.1002/cphc.202200828, 10.1002/cphc.202200827

Tags

isotope effects, ionic liquids, hydrogen bonding, solid state NMR spectroscopy, thermodynamics

Authors

Khudozhitkov Alexander E. ^1,2 , Stange Peter ³ , Paschek Dietmar ³ , Stepanov Alexander G. ¹ , Kolokolov Daniil I. ^1,2 , 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, AlbertEinstein-Straße 27, 18059 Rostock, Germany
4	Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany

Funding (3)

1	Russian Science Foundation	21-13-00047
2	German Research Foundation	LU 506/15 (401427621)
3	Alexander von Humboldt Foundation

We report strong isotope effects for the protic ionic liquid triethylammonium methanesulfonate [TEA][OMs] by means of deuterium solid-state NMR spectroscopy covering broad temperature ranges from 65 K to 313 K. Both isotopically labelled PILs differ in non-deuterated and fully deuterated ethyl groups of the triethyl ammonium cations. The N-D bond of both cations is used as sensitive probe for hydrogen bonding and structural ordering. The 2 H NMR line shape analysis provides the deuteron quadrupole coupling constants and the characteristics of a broad heterogeneous phase with simultaneously present static and mobile states indicating plastic crystal behavior. The temperatures where both states are equally populated differ by about 80 K for the two PILs, showing that deuteration of the ethyl groups in the trialkylammonium cations tremendously shifts the equilibrium towards the static state. In addition, it leads to a significant less cooperative transition, associated with a significantly reduced standard molar transition entropy.

Khudozhitkov A.E. , Stange P. , Paschek D. , Stepanov A.G. , Kolokolov D.I. , Ludwig R.
The Influence of Deuterium Isotope Effects on Structural Rearrangements, Ensemble Equilibria, and Hydrogen Bonding in Protic Ionic Liquids
ChemPhysChem. 2022. V.23. N23. e202200557 :1-6. DOI: 10.1002/cphc.202200557, 10.1002/cphc.202200828, 10.1002/cphc.202200827 WOS Scopus РИНЦ РИНЦ РИНЦ ANAN PMID OpenAlex

Submitted:	Jul 28, 2022
Accepted:	Aug 8, 2022
Published online:	Aug 9, 2022
Published print:	Dec 5, 2022

Web of science:	WOS:000849808100001
Scopus:	2-s2.0-85137356034
Elibrary:	50783470 \| 59515893 \| 58673988
Chemical Abstracts:	2022:2322774 \| 2022:3012097
PMID:	35944124
OpenAlex:	W4292457893

DB	Citing
Scopus	2
OpenAlex	1
Elibrary	1