Ion Mobility in Hydroxy-Functionalized Ionic Liquids Depends on Cationic Clustering: Tracking the Alkyl Chain Length Behavior with Deuteron NMR Relaxation | Sciact - CRIS-system of Boreskov Institute of Catalysis

Ion Mobility in Hydroxy-Functionalized Ionic Liquids Depends on Cationic Clustering: Tracking the Alkyl Chain Length Behavior with Deuteron NMR Relaxation Full article

Journal

The Journal of Physical Chemistry B
ISSN: 1520-6106 , E-ISSN: 1520-5207

Output data

Year: 2023, Volume: 127, Number: 43, Pages: 9336–9345 Pages count : 10 DOI: 10.1021/acs.jpcb.3c05330

Authors

Khudozhitkov Alexander E. ^1,2 , 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	Department LL&M, University of Rostock, Albert-Einstein-Str. 25, 18059 Rostock, Germany
4	Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany

Funding (5)

1	Russian Science Foundation	21-13-00047
2	German Research Foundation	LU 506/15 (401427621)
3	German Research Foundation	LU 506/14-2 (286149019)
4	Alexander von Humboldt Foundation
5	Ministry of Science and Higher Education of the Russian Federation	0239-2021-0003

Observing and quantifying the like-charge attraction in liquids and solutions is still challenging. However, we showed that elusive cation–cation hydrogen bonding may govern the structure and interaction in hydroxyl-functionalized ionic liquids. Therefore, cationic cluster formation depends on the shape, charge distribution, and functionality of the ions. We demonstrated by means of solid-state 2H NMR spectroscopy that cationic clusters change the structure and dynamics of ionic liquids. With increasing alkyl chain length, we observed two deuteron quadrupole coupling constants for the OD groups, differing by about 30 kHz. The lower value was assigned to the cation–cation interaction, indicating that the average (c–c) hydrogen bonds are stronger than the (c–a) hydrogen bonds between the cation and the anion despite the repulsive and attractive Coulomb interaction in the first and latter cases. Ion mobility could be studied by 2H NMR spectroscopy, although the deuterons in the hydrogen-bonded clusters underwent fast exchange. Our results also showed that simple relaxation models are not applicable anymore and that anisotropic motion must be considered.

Khudozhitkov A.E. , Stepanov A.G. , Kolokolov D.I. , Ludwig R.
Ion Mobility in Hydroxy-Functionalized Ionic Liquids Depends on Cationic Clustering: Tracking the Alkyl Chain Length Behavior with Deuteron NMR Relaxation
The Journal of Physical Chemistry B. 2023. V.127. N43. P.9336–9345. DOI: 10.1021/acs.jpcb.3c05330 WOS Scopus РИНЦ AN PMID OpenAlex

Submitted:	Aug 7, 2023
Accepted:	Sep 24, 2023
Published online:	Oct 19, 2023
Published print:	Nov 2, 2023

Web of science:	WOS:001096330800001
Scopus:	2-s2.0-85175878316
Elibrary:	55291189
Chemical Abstracts:	2023:2148272
PMID:	37857325
OpenAlex:	W4387769163

DB	Citing
OpenAlex	5
Scopus	6
Web of science	6
Elibrary	5