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

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

Journal

The Journal of Physical Chemistry Letters
ISSN: 1948-7185

Output data

Year: 2018, Volume: 9, Number: 16, Pages: 4607-+ Pages count : DOI: 10.1021/acs.jpclett.8b02097

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	(Данные Web of science) Int Tomog Ctr SB RAS, Inst Skaya St 3a, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Pirogova St 2, Novosibirsk 630090, Russia
3	(Данные Web of science) Boreskov Inst Catalysis SB RAS, Lavrentiev Ave 5, Novosibirsk 630090, Russia
4	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Lavrentiev Ave 9, Novosibirsk 630090, Russia
5	(Данные Web of science) Inst Automat & Electrometry SB RAS, Koptyug Ave 1, Novosibirsk 630090, Russia
6	(Данные Web of science) Voevodsky Inst Chem Kinet & Combust SB RAS, Inst Skaya St 3, Novosibirsk 630090, Russia

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 (T-g) 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 T-g, which exist in a rather broad temperature range of similar to 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 T-g 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
The Journal of Physical Chemistry Letters. 2018. V.9. N16. P.4607-+. DOI: 10.1021/acs.jpclett.8b02097 WOS Scopus РИНЦ

Published online:	Jul 27, 2018
Published print:	Aug 16, 2018

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