Insight into local structure and molecular dynamics in organic solid-state ionic conductors

Chemphyschem. 2014 Dec 1;15(17):3720-4. doi: 10.1002/cphc.201402487. Epub 2014 Sep 18.

Abstract

Elucidating the rate and geometry of molecular dynamics is particularly important for unravelling ion-conduction mechanisms in electrochemical materials. The local molecular motions in the plastic crystal 1-ethyl-1-methylpyrrolidinium tetrafluoroborate ([C2 mpyr][BF4 ]) are studied by a combination of quantum chemical calculations and advanced solid-state nuclear magnetic resonance spectroscopy. For the first time, a restricted puckering motion with a small fluctuation angle of 25° in the pyrrolidinium ring has been observed, even in the low-temperature phase (-45 °C). This local molecular motion is deemed to be particularly important for the material to maintain its plasticity, and hence, its ion mobility at low temperatures.

Keywords: NMR spectroscopy; chemical shift anisotropy; molecular dynamics; plastic crystals; quantum chemical calculations.