Ryosuke Taniki

Highly Conductive Plastic Crystals Based on Fluorohydrogenate Anions

The new ionic plastic crystals N,N-dimethylpyrrolidinium fluorohydrogenate [DMPyr(FH)(2)F] and N-ethyl-N-methylpyrrolidinium fluorohydrogenate [EMPyr(FH)(2)F] were prepared, and their physicochemical, structural, and electrochemical properties were investigated. The DMPyr(FH)(2)F and EMPyr(FH)(2)F salts exhibited small entropy changes of melting, 4.1 and 2.0 J K(-1) mol(-1), respectively, and had ionic plastic crystal phases in the temperature ranges of 258-325 and 236-303 K, respectively. These phases had NaCl-type structures; the lattice constants were 9.90 Å for DMPyr(FH)(2)F and 10.18 Å for EMPyr(FH)(2)F. The ionic conductivities of the ionic plastic crystal phases ranged from 10(0) to 10(1) mS cm(-1) [e.g., 10.3 mS cm(-1) at 298 K for DMPyr(FH)(2)F and 14.4 mS cm(-1) at 288 K for EMPyr(FH)(2)F]. Pulsed-field gradient spin-echo NMR spectroscopy revealed that only the anion could move in the ionic plastic crystal phase as a charge carrier with a diffusion coefficient of ~10(-7) cm(2) s(-1). The self-diffusion coefficient of the cation in the ionic plastic crystal phase of DMPyr(FH)(2)F was too small to measure, although the cation in EMPyr(FH)(2)F had a slight mobility below 303 K.