GHCA undergoes four phase transitions at Tc1 = 402 K, Tc2 = 373 K, Tc3 = 162 K, and Tc4 = 146 K. Below Tc3 it possesses pyroelectric properties with the spontaneous polarization vector (Ps) in the ac plane and the maximum along the c axis equal to 8 μC/m2. Dielectric dispersion studies of GHCA show that the main dielectric dispersion connected probably with collective motions of chlorine ions is above 1GHz. For the phase transition at Tc2 to a superionic phase the thermal dilatation and electric conductivity were measured. The anomalies of the electric conductivity at Tc2 and Tc1 were observed with large values of σ(10-3 S/m) above Tc3. The guanidinium cations above Tc2, besides reorientational motions, undergo slow self diffusion.
Dielectric, DSC, thermal expansion and preliminary X-ray diffraction studies on (n-C3H7NH3)- SbBr5 are reported. It was found that this crystal undergoes a complex sequence of phase transitions. On cooling: phase I → phase II at 188.7 K (continuous), II → III at 165 K (1st order, ΔS = 26.8 J/mol K), III → IV at 137 K (1st order, 1.6 J/mol K). On heating: IV → III at 154 K, III → II’ at 168 K, II’ → II at 177 K (1st order, 2.8 J/mol K), II → I at 189 K. All 1st order phase transitions are likely due to the motion of the n-C3H7NH3+cations. The dielectric dispersion studies between 100 Hz-1 MHz within the phases I and II indicate a fast reorientational motion of dipoles with τ < 10−7 S.