Low-Frequency Spectra of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Poly(ethylene glycol) by Femtosecond Raman-Induced Kerr Effect Spectroscopy

Abstract

This is the first report on low-frequency spectra of ionic liquid (IL)/polymer mixtures using femtosecond Raman-induced Kerr effect spectroscopy. We studied mixtures of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm][BF4]) and poly(ethylene glycol) (PEG) with Mn = 400 (PEG400) at various concentrations. To elucidate the unique features of the IL/polymer mixture system, mixtures of PEG400 with a molecular liquid, 1-octhylimidazole (OIm), which is a neutral analog of the cation, were also studied. In addition, mixtures of [MOIm][BF4] with ethylene glycol (EG) and poly(ethylene glycol) with Mn = 4000 (PEG4000) were also investigated. The first moments of broad low-frequency spectra, mainly due to intermolecular vibrations for the [MOIm][BF4]/PEG400 and OIm/PEG400, increased slightly with increasing concentration of PEG400, indicating that microscopic intermolecular interactions, in general, are slightly enhanced. We also compared the [MOIm][BF4] mixtures with EG, PEG400, and PEG4000 at concentrations of 5 and 10 wt % PEG or EG. The low-frequency spectra of samples with the same concentrations were quite similar, but a comparison of the normalized spectra showed that the spectral intensity in the low-frequency region below ∼50 cm-1 of the [MOIm][BF4] mixtures with PEG400 and PEG4000 is somewhat lower than that of the [MOIm][BF4] mixtures with EG. Although the effect of the polymer is small compared to other polymer solution systems, this feature is attributed to a suppression of translational motion in the mixtures of [MOIm][BF4] with PEG compared to the mixtures of [MOIm][BF4] with EG due to the greater mass of PEG than EG. Density, surface tension, viscosity, and electrical conductivity were also estimated. From Walden plots, it was found that the [MOIm][BF4]/PEG4000 system showed more ideal electrical conductive behavior than the [MOIm][BF4]/PEG400 and [MOIm][BF4]/EG systems.