On the basis of dilatometric, optical, and dielectric investigations of (NH3C2H5)2CuC14 crystals the existence of phase transitions at T1 = 364 and T2 = 356 K was confirmed. Anomalous behaviour of the thermal expansion coefficient and optical birefringence around T3 = 330 K was related to earlier unknown phase transition. Besides, it was shown that these crystals are characterised by considerable protonic conductivity, the nature of which is fairly well explained in the framework of Grotthus mechanism of proton transport.

Abstract. We report on the growth and initial thermal and optical characterisation of a single-crystalline ternary halide, Tl 4 CdI 6 . The crystal is described by the centrosymmetric tetragonal class P4/mnc at the room temperature. The parameters of linear thermal expansion are studied in the temperature region 330-500 K. The crystal is optically positive and reveals very high optical anisotropy (the birefringence ~ 0.13 at 633 nm). Its optical pseudo-gap value corresponds to widegap semiconductors. A broad maximum at 400-410 K found in the temperature dependence of IR radiation-induced second harmonic generation may be indication of a polymorphic phase transformation.

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On the basis of dilatometric and dielectric investigations of NH(CH3)3CuCl3 · 2H2O crystals the earlier unknown phase transition with considerable temperature hysteresis was found at T c 1 = 198 K and T h 1 = 223 K, respectively, in cooling and heating runs. Existence of the characteristic dielectric dispersion was revealed within the high-temperature phase. It corresponds to the single dielectric relaxator below 250 K as well as to co-existence of two relaxators above this temperature. The determined values of the activation energy and relaxation time are characteristic of the co-operative reorientation of the trimethylammonium cation (high-frequency relaxator) whereas the combined reorientation motions of the CuCl 2 · 2H 2 O chains would be responsible for the low-frequency relaxation process. It was found that the above mentioned quasi-Debye type processes are involved into the mechanisms of the protonic conductivity.

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