Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR
Научная публикация
| Общая информация |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Journal of Physical Chemistry Letters
ISSN: 1948-7185
|
| Вых. Данные |
Год: 2018,
Том: 9,
Страницы: 4607-4612
Страниц
: 6
DOI:
10.1021/acs.jpclett.8b02097
|
| Ключевые слова |
Electron spin resonance spectroscopy Glass Ionic liquids Molecular dynamics Paramagnetic resonance
Stereochemistry |
| Авторы |
Ivanov Mikhail Yu.
1,2
,
Prikhod'ko Sergey A.
3
,
Adonin Nicolay Yu.
3
,
Kirilyuk Igor A.
4
,
Adichtchev Sergey V.
5
,
Surovtsev Nikolay V.
5
,
Dzuba Sergei A.
6
,
Fedin Matvey V.
1,2
|
| Организации |
| 1 |
International Tomography Center SB RAS, Institutskaya Street 3a, 630090 Novosibirsk, Russia
|
| 2 |
Novosibirsk State University, Pirogova Street 2, 630090 Novosibirsk, Russia
|
| 3 |
Boreskov Institute of Catalysis SB RAS, Lavrentiev Avenue 5, 630090 Novosibirsk, Russia
|
| 4 |
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, Lavrentiev Avenue 9, 630090 Novosibirsk, Russia
|
| 5 |
Institute of Automation and Electrometry SB RAS, Koptyug Avenue 1, 630090 Novosibirsk, Russia
|
| 6 |
Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, Institutskaya Street 3, 630090 Novosibirsk, Russia
|
|
Информация о финансировании (2)
|
1
|
Российский научный фонд
|
14-13-00826
|
|
2
|
Федеральное агентство научных организаций России
|
0333-2017-0002
|
Unusual physical and chemical properties of ionic liquids (ILs) open up prospects for various applications. We report the first observation of density/rigidity heterogeneities in a series of ILs near the glass transition temperature (Tg) by means of pulse electron paramagnetic resonance (EPR). Unprecedented suppression of molecular mobility is evidenced near the glass transition, which is assigned to unusual structural rearrangements of ILs on the nanometer scale. Indeed, pulse and continuous wave EPR clearly indicate the occurrence of heterogeneities near Tg, which exist in a rather broad temperature range of ∼50 K. The two types of local environments are evidenced, being drastically different by their stiffness. The more rigid one suppresses molecular mobility, whereas the softer one instead promotes diffusive molecular rotation. Such properties of ILs near Tg are of general importance; moreover, the observed density/rigidity heterogeneities controlled by temperature might be considered as a new type of tunable reaction nanoenvironment.