Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR | Sciact - CRIS-system of Boreskov Institute of Catalysis

Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR Full article

Journal

Journal of Physical Chemistry Letters
ISSN: 1948-7185

Output data

Year: 2018, Volume: 9, Pages: 4607-4612 Pages count : 6 DOI: 10.1021/acs.jpclett.8b02097

Tags

Electron spin resonance spectroscopy Glass Ionic liquids Molecular dynamics Paramagnetic resonance Stereochemistry

Authors

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

Affiliations

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

Funding (2)

1	Russian Science Foundation	14-13-00826
2	Federal Agency for Scientific Organizations	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.

Ivanov M.Y. , Prikhod'ko S.A. , Adonin N.Y. , Kirilyuk I.A. , Adichtchev S.V. , Surovtsev N.V. , Dzuba S.A. , Fedin M.V.
Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR
Journal of Physical Chemistry Letters. 2018. V.9. P.4607-4612. DOI: 10.1021/acs.jpclett.8b02097 WOS Scopus РИНЦ ANCAN PMID OpenAlex

Submitted:	Jul 4, 2018
Accepted:	Jul 27, 2018
Published online:	Jul 27, 2018
Published print:	Aug 16, 2018

Web of science:	WOS:000442446900022
Scopus:	2-s2.0-85051137186
Elibrary:	35732483
Chemical Abstracts:	2018:1401962
Chemical Abstracts (print):	169:242516
PMID:	30052047
OpenAlex:	W2884948680

DB	Citing
Web of science	34
Scopus	33
Elibrary	34
OpenAlex	35