ABSTRACTThermotropic liquid-crystalline behavior of various complex salts, which are structurally simple amphiphiles without rigid cores, was evaluated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffractometry. The phosphonium salts, consisting of positive phosphorus and negative chloride ions, were found to show a smectic A phase in which a homeotropic structure was formed spontaneously. It is significant that the phosphonium salts possess an advantageous feature as thermotropic liquid crystals and show a stable liquid-crystalline phase and a simple phase transition behavior in comparison with commonly available ammonium analogs. Furthermore, the introduction of divalent metal ions into the amphiphiles was revealed to result in enhancement of the thermal properties. Although the ammonium chlorides as parent compounds showed no liquid-crystalline phase (or indistinct transition behavior), the ammonium complexes possessing tetrachlorometalate ions exhibited clearly the smectic A phase in the expanded temperature range. Additionally, through the evaluation of dipolar alignment in the solid-state phosphonium assembly by second harmonic generation, it was assumed that the self-assembly can be regarded as layered polar thin films produced by two-dimensional ionic layers with an overall permanent electric polarization.
XRDUA: crystalline phase distribution maps by two-dimensional scanning and tomographic (micro) X-ray powder diffraction