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Volumetric and x-ray investigations of the crystalline and columnar phases of copper (II) soaps under pressure

Physical Review A, ISSN: 1050-2947, Vol: 46, Issue: 12, Page: 7643-7651
1992
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Binuclear copper (II) carboxylates, Cu2(CnH2n+1O2)4, crystallize at room temperature in layered systems in which planes of polar cores are separated by a double layer of alkyl chains. These compounds are mesomorphic in nature above ca. 100 °C. Pseudopolymeric chains of regularly stacked binuclear cores are located at the nodes of a two-dimensional hexagonal lattice and are surrounded by disordered aliphatic chains. The transition from the crystal to the columnar mesophase is characterized by a change in the repeat distance of the binuclear cores along the pseudopolymeric axis. In the crystalline phase, these cores are all oriented in the same direction with a repeat distance of 5.2; in the columnar mesophase, the polar cores are perpendicular to the columnar axis and superposed in a fourfold helicoidal fashion, at least on a local scale, with a repeat distance of 4.7. We present here the effect of pressure on these anisotropic systems in a direction parallel to the columnar axis, and in the plane of the two-dimensional lattice. In a first part, we report the pressure-volume-temperature (P-V-T) relationship of these compounds (n=12, 18, and 24) in the temperature range from 30 to 200 °C, and in the pressure range from 1 to 2000 bars. Isothermal compressibility and isobaric expansion are determined in the crystalline and mesomorphic phases. In the mesophase, pressure-volume isotherms can be described by the Tait equation, as in most liquids or molten polymers. In a second part, we discuss the x-ray-diffraction experiments performed under pressure. In the mesophase, the area of the two-dimensional lattice decreases with increasing pressure and, at sufficiently high pressure, the columnar mesophase transforms into a crystalline lamellar phase. By combining P-V-T and x-ray results, we deduce an increase of the stacking period of the binuclear cores as a function of increasing pressure. © 1992 The American Physical Society.

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