Controlling the Melting Temperatures and Ion Dynamics of Carboxy-Functionalized Ionic Liquids
Научная публикация
| Журнал |
The Journal of Physical Chemistry B
ISSN: 1520-6106
, E-ISSN: 1520-5207
|
| Вых. Данные |
Год: 2025,
Том: 129,
Номер: 44,
Страницы: 11557-11563
Страниц
: 7
DOI:
10.1021/acs.jpcb.5c05946
|
| Авторы |
Khudozhitkov Alexander E.
1,2
,
Hunger Lasse
3
,
Al Sheakh Loai
3
,
Stepanov Alexander G.
1
,
Kolokolov Daniil I.
1,2
,
Ludwig Ralf
3,4,5
|
| Организации |
| 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 |
Institut für Chemie, Physikalische und Theoretische Chemie, Universität Rostock, Albert-Einstein-Straße 27, Rostock 18059, Germany
|
| 4 |
Department LL&M, University of Rostock, Albert-Einstein-Str. 25, Rostock 18059, Germany
|
| 5 |
Leibniz-Institut für Katalyse an der Universität Rostock, e.V. Albert-Einstein-Str. 29a, Rostock 18059, Germany
|
|
Информация о финансировании (3)
|
1
|
Российский научный фонд
|
24-13-00129 (124061400012-7)
|
|
2
|
German Research Foundation
|
LU 506/17-1 (Project 470038970)
|
|
3
|
German Research Foundation
|
LU-506/18-1 (Project 517661181)
|
We measured the 2H spectra of carboxy-functionalized ionic liquids [Py-(CH2)n-COOD][NTf2] with alkyl chains n = 1,2,4,5,6,7,9 by means of NMR solid-state spectroscopy. The change from the broad Pake patterns in the glassy state to the narrow lines in the liquid with increasing temperatures indicated the glass–liquid phase transition and allowed the determination of the melting temperatures Tm of these unique ILs characterized by the formation of doubly hydrogen-bonded cationic dimers (c+═c+) present in the gas, as well as in the condensed phases. The melting occurs at 248 K, only 30 K above the glass transition temperature Tg. The Tm/Tg ratio is 1.13 and thus significantly smaller than the reported values for H-bonded molecular liquids such as water and alcohols. The small ratio is usually referred to the dynamical heterogeneities in the liquid material, which is illustrated by the simultaneously observed solid and liquid NMR spectra. Additionally, we measured the NMR relaxation times T1 and T2 that could be modeled by a slow isotropic and a fast anisotropic motion. The maximum between the two T1 minima coincides with the observed melting temperatures. The microscopic ILs viscosity reflected by the cation dynamics reaches optimal values for n > 4. Our results show that the doubly H-bonded carboxy-functionalized ILs provide low melting temperatures and thus might be suitable for electrolytes.