Solid state 1H, 7Li, and 13C NMR studies on new ionic plastic crystals of crown ether–Li-TFSA complexes

Abstract

This study provides the first evidence that a Li ion can form ionic plastic crystals using crown ether with a bis-(trifluoromethanesulphonyl) amide (TFSA) anion. ¹H, ⁷Li, and ¹³C nuclear-magnetic-resonance (NMR) measurements of the 15-crown-5–Li-TFSA complex revealed that the constituents underwent isotropic reorientation in the plastic crystalline phase. The NMR data of the 12-crown-4–Li-TFSA salt showed that the complex is a rotator crystal (the complexes are denoted as [Li 15C5] and [Li 12C4] in this paper). The X-ray diffraction (XRD) reflection patterns of the [Li 15C5] crystal recorded in the highest-temperature solid phase (plastic phase) could be indexed to a cubic structure. Conversely, [Li 12C4] could be fitted to a trigonal structure. In this study, [M (3n)Cn] (M = Li, Na, K; n = 4–6) complexes were also prepared, and NMR, DSC, XRD, and electrical conductivity measurements were performed. Based on these results, we additionally revealed that the [Na 15C5] and [K (15C5)₂] complexes are also new rotator crystals. Single-crystal XRD measurements also revealed that the [Na 15C5] compound has two stable sites in the crystal. Activation energies of molecular motions in the [M (3n)Cn] crystals were estimated using ¹H NMR relaxation time (T₁ and T₂) measurements. The electrical conductivity measurements of [Li 12C4], [Li 15C5], and [Na 15C5] showed high ionic conductivities (∼10⁻² S cm⁻¹).