Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 25, Issue 40, Pages 27836-27847Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3cp02614k
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This study provides the first evidence that lithium ions can form ionic plastic crystals using crown ether with a bis-(trifluoromethanesulphonyl) amide (TFSA) anion. Various measurements, including nuclear-magnetic-resonance, X-ray diffraction, and electrical conductivity, were conducted to investigate the properties of these crystals. The study also discovered new rotator crystals and estimated the activation energies of molecular motions in the crystals.
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. H-1, Li-7, and C-13 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 H-1 NMR relaxation time (T-1 and T-2) measurements. The electrical conductivity measurements of [Li 12C4], [Li 15C5], and [Na 15C5] showed high ionic conductivities (similar to 10(-2) S cm(-1)).
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