Novel ionic plastic phase of [(CH3)4N]SCN obtainable above 455 K studied by proton magnetic resonance, electrical conductivity and thermal measurements
作者： Toshitaka Tanabe , Daiyu Nakamura , Ryuichi Ikeda
DOI: 10.1039/FT9918700987
关键词: Tetramethylammonium 、 Thiocyanate 、 Ionic bonding 、 Electrical resistivity and conductivity 、 Phase transition 、 Analytical chemistry 、 Plastic crystal 、 Activation energy 、 Chemistry 、 Proton NMR 、 Physical and Theoretical Chemistry
摘要: A new high-temperature solid phase of tetramethylammonium thiocyanate has been found above the transition at 455 K, where a large entropy change (15 J K–1 mol–1) was observed. X-ray powder patterns recorded ca. 470 K showed that this forms CsCl-type cubic lattice with aO= 600 pm, indicating SCN– anions take highly disordered orientations. The presence rapid three-dimensional self-diffusion, as well overall rotation cations in phase, revealed by measurements 1H NMR spin–lattice relaxation times, T1 and T1ρ, second moment absorptions electrical conductivity. ionic-diffusion constant (of order 10–13 m2 s–1) obtained around 490 is roughly same those reported for ‘ionic plastic’ crystals. An activation energy 110 kJ mol–1 determined cationic self-diffusion. These results imply first example an ionic plastic crystal containing cations.
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