Phase transitions and anionic dynamics of dimethylammonium hexachlorotellurate(IV) as studied by pulsed nuclear quadrupole resonance of chlorine

Abstract

The temperature dependence of 35Cl NQR frequencies has been reinvestigated for dimethylammonium hexachlorotellurate(IV) using an FT NQR spectrometer. A new line is observed just above the lowest-frequency line already reported for the intermediate-temperature phase. In the lowest-temperature phase, the temperature dependence is definitely determined by finding new lines. The NQR frequencies can be precisely measured even in the vicinity of the phase transitions. The temperature dependence of the nuclear quadrupole relaxation time, T 1Q of 35Cl and 37Cl nuclei has also been observed. In a temperature range 64–160 K, the isotope ratio, T 1Q( 37Cl)/ T 1Q( 35Cl) is 1.5 for each line, suggesting that the quadrupolar relaxation arises mainly from the libration of the complex anion. Above 160 K, T 1Q decreases very rapidly with increasing temperature for each line. This can be interpreted in terms of the onset of the reorientation of the anion as a whole, which is responsible for the fade-out phenomenon of the two lines occurring near 220 K. The nature of the phase transitions and the anionic dynamics are discussed in detail. Especially, the phase transition at 96 K which is rather unusual and is explained through softening of the librations and the rotational displacement of the anions successively operated.