Phase transition and anionic motion in solid [(CH3)2NH2]2SnCl6 as studied by the temperature dependence of 35Cl NQR frequencies and chlorine nuclear relaxation times determined with a pulsed NQR spectrometer

Abstract

AbstractThe temperature dependence of 35Cl NQR frequencies of [(CH3)2NH2]2SnCl6 was precisely determined between 78 and ca. 250 K. by means of an FT NQR spectrometer. The high‐frequency line of the two 35Cl NQR signals having the intensity ratio of 2:1 already reported was observed to be split below 102 K. into sharp and broad lines with approximately equal integrated intensify. This clearly indicates the occurrence of a structural phase transition of a second‐order nature at this temperature. The presence of phase transition around this temperature has been anticipated from the IR and NQR studies previously done. The temperature dependence of chlorine nuclear spin‐lattice relaxation time, T1Q shows a dip with a clear depression at 102 K. The mechanism of the phase transition is discussed from the T1Q results and the fact that the frequency separation of the doublet increases with decreasing temperature. Above 180 K, T1Q of both lines decreased rapidly and the log T1Q vs. T−1 curves were almost linear. This decrease of T1Q was explained through the onset of the C4 reorientation of the anions with the activation energy of ca. 35 kJ mol−1. The fade‐out phenomenon of the two NQR lines occurring far below room temperature can be well explained by the onset of the above motion with the very low activation energy.