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

Mikhail Yu Ivanov, Sergey A. Prikhod'Ko, Nicolay Yu Adonin, Igor A. Kirilyuk, Sergey V. Adichtchev, Nikolay V. Surovtsev, Sergei A. Dzuba, Matvey V. Fedin

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)4607-4612
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume9
Issue number16
DOIs
Publication statusPublished - 16 Aug 2018

Keywords

  • TIME-RESOLVED EPR
  • SPATIAL HETEROGENEITY
  • CHARGE-TRANSPORT
  • NMR-SPECTROSCOPY
  • SPIN DYNAMICS
  • TEMPERATURE
  • WATER
  • CATALYSIS
  • ECHO
  • TETRAFLUOROBORATE

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