A new class of organic ionic plastic crystals was discovered. A series of alkylene 1,2-bis[N-(N′-alkylimidazolium)] salts with Br- and PF6- anions was prepared and most of the ethylene (C 2) linked compounds undergo multiple solid-solid phase transitions as determined by differential scanning calorimetry (DSC). The salts with longer spacers (C3 or C4) between the imidazolium units do not display any solid-solid transitions. The PF6- salts with terminal C10 and C12n-alkyl moieties are "classical" organic ionic plastic crystals by Timmermans' definition; they have low ΔSf (11 J K-1 mol-1 for C10 and 12 J K-1 mol-1 for C12). Additionally, the C2 linked bis-imidazolium salts with n-butyl, n-hexyl, n-heptyl and n-octyl termini all undergo two, three or four solid state transitions and exhibit ΔSf values in the range of 36-49 J K-1 mol-1, which are similar to those of other known ionic plastic crystalline materials. These materials were additionally characterized via ionic conductivity and solid state NMR. These ionic plastic crystals are presumably single-ion conductors, but the ionic conductivities appear to be too low for practical applications. The activation energy for conduction decreases as these compounds are heated through each solid-solid transition. The lack of any change in solid state 2H NMR spectra with temperature indicates that there is no change in phenyl ring flipping, suggesting no change in the imidazolium local environment. A resolution of this apparent dichotomy is perhaps that the counterions reside with the ethylene spacers between imidazolium moieties.
All Science Journal Classification (ASJC) codes
- Materials Chemistry