Phase behaviour of the thermotropic cubic mesogen 1,2-bis-(4- n -octyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis-(4-n-octyloxybenzoyl)hydrazine, BABH(8), was investigated under pressures up to 200 MPa using a high pressure differential thermal analyser, wide-angle X-ray diffraction and a polarizing optical microscope equipped with a high pressure optical cell. The phase transition sequence, low temperature crystal (Cr₂)-high temperature crystal (Cr ₁)- cubic (Cub)-smectic C (SmC)-isotropic liquid (I) observed at atmospheric pressure, is seen in the low pressure region below about 30 MPa. The cubic phase disappears at high pressures above 30–40 MPa, in conjunction with the disappearance of the Cr₁ phase. The transition sequence changes to Cr₂-SmC-I in the high pressure region. Since only the Cub-SmC transition line among all the phase boundaries has a negative slope (dT/dP) in the temperature-pressure phase diagram, the temperature range for the cubic phase decreases rapidly with increasing pressure. As a result, a triple point was estimated approximately as 31.6 ±2.0 MPa, 147.0±1.0°C for the SmC, Cub and Cr₁ phases, indicating the upper limit of pressure for the observation of the cubic phase. Reversible changes in structure and optical texture between the Cub and SmC phases were observed from a spot-like X-ray pattern and dark field for the cubic phase to the Debye-Sherrer pattern and sand-like texture for the SmC phase both in isobaric and isothermal experiments.     

Thermodynamic investigation of the thermotropic cubic mesogen, 1,2-bis(4- n -octyloxybenzoyl)hydrazine

Themolar heat capacity of the thermotropic cubic mesogen 1,2-bis(4- n -alkoxybenzoyl)hydrazine, BABH(8) for short, with a purity of 99.43 mol% has been precisely measured with an adiabatic calorimeter at temperatures between 14 and 480 K. The enthalpy and entropy gained at each phase transition across the phase sequence of \[crystal(2) crystal(1) cubic mesophase SmC isotropic liquid] have been determined. The existence of a solid-to-solid phase transition with a fairly large entropy change seems to be necessary for the alkyl moieties attached to both sides of the molecule to play the role of 'solvent' in the cubic mesophase. On the basis of curvature elasticity considerations, the small energy difference between the cubic and SmC phases is favourably accounted for in terms of the jointed-rod micelles model. The reason for the immiscibility of BABH(8) with the cubic D mesogen, 4- n -hexadecyloxy-3- nitrobiphenyl-4-carboxylic acid is discussed in terms of the large difference in their molecular size and of 'structure breaking' arising from the admixture of heterogeneously hydrogen-bonded materials.     

Phase behaviour of the thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine under pressure

The phase transition behaviour of an optically isotropic, thermotropic cubic mesogen 1,2-bis(4-n-decyloxybenzoyl)hydrazine, BABH(10), was investigated under pressures up to 300 MPa using a high pressure differential thermal analyser, a wide angle X-ray diffractometer and a polarizing optical microscope (POM) equipped with a high pressure optical cell. The reversible change in structure and optical texture between the cubic (Cub) and smectic C (SmC) phases was associated with a change from a spot-like X-ray pattern and dark field for the Cub phase to the Debye-Sherrer ring pattern and sand-like texture for the SmC phase under both isobaric and isothermal conditions. The Cub phase was found to disappear at pressures above about 11 MPa. The phase transition sequence, low temperature crystal (Cr₃)-intermediate temperature crystal (Cr₂)-high temperature crystal (Cr₁)-Cub-SmC-isotropic liquid (I) observed at atmospheric pressure, is maintained in the low pressure region below 10 MPa. The transition sequence changes to Cr₃-Cr₂-(Cr₁)-SmC-I in the high pressure region. Since the Cub-SmC transition line determined by POM has a negative slope (dT/dP) in the T-P phase diagram, a triple point is estimated approximately at 10-11 MPa, and 143-145°C for the SmC, Cub and Cr₁ phases, giving the upper limit of pressure for the observation of the cubic phase.     

Phase behaviour of the thermotropic cubic mesogens 1,2-bis-(4-n-undecyl- and 4-n-dodecyl-oxybenzoyl)hydrazine under pressure

The phase transition behaviour of two optically isotropic, thermotropic cubic mesogens 1,2-bis-(4-n-undecyloxy- and 4-n-dodecyloxy-benzoyl)hydrazine, BABH(11) and BABH(12), was investigated under hydrostatic pressures up to 300 MPa using a high pressure differential thermal analyser, a wide angle X-ray diffractometer and a polarizing optical microscope equipped with a high pressure optical cell. It is found that for BABH(11) and BABH(12), a smectic C (SmC) phase is induced between the isotropic liquid (I) and the cubic (Cub) phases by applying pressures above 10-12 and 16-17 MPa, respectively. A sea-island texture consisting of bright sand-like sea regions (SmC phase) and areas of dark islands (Cub phase) appears in the mesophase under pressures up to 140 MPa, while the sand-like texture of the SmC phase is formed predominantly on cooling under pressure. These observations indicate the destabilization of the cubic phase with increasing pressure. The phase transition sequence of BABH(11) and BABH(12), Cr-Cub-I at atmospheric pressure, changes to Cr-Cub-SmC-I under intermediate pressures and would change to Cr-SmC-I under elevated pressure.     

Thermal behaviour under pressure of the thermotropic cubic mesogen 4'- n -alkoxy-3'-nitrobiphenyl-4-carboxylic acids

The thermal behaviour of members of a homologous series which exhibits the optically isotropic cubic phase, the 4'- n -alkoxy-3'-nitrobiphenyl-4-carboxylic acids having alkoxy chains containing 16, 20 and 22 carbon atoms (referred to as ANBC-16, -20 and -22, respectively) was investigated under pressures up to 200-400 MPa by high pressure differential thermal analysis. In the phase diagram of ANBC-16 obtained on heating, a triple point was estimated at 54 ±1 MPa and 205 ±1°C for the SmC, Cub and SmA phases. It was found that the X phase is formed on cooling under all pressures, while appearing on heating at high pressures above about 54 MPa. Thus the X phase appears monotropically between the SmA and Cub phases in the low pressure region and enantiotropically between the SmA and SmC phases under higher pressures. It is strongly suggested that the X phase is a columnar mesophase. For ANBC-20 and -22, the cubic phase tends to be destabilized with increasing pressure. The temperature region of the cubic phase of ANBC-20 becomes narrower with increasing pressure and a triple point for the SmC, Cub and I phases is estimated to be at about 309 MPa. On the other hand, the cubic phase of ANBC-22 is still observed at the highest pressure examined.     

Thermal behaviour of the thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) under hydrostatic pressure

The phase behaviour of 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using high pressure differential thermal analysis. The phase transition sequence crystal 4 (Cr4)-crystal 3 (Cr3)-crystal 2 (Cr₂)-crystal 1 (Cr₁)-smectic C (SmC)-Cubic (Cub)-smectic A (SmA)-'structured liquid' (I₁)-isotropic liquid (I₂) was observed for a virgin sample on heating at atmospheric pressure. The stable temperature region of the optically isotropic cubic phase becomes narrower on increasing pressure and disappears at pressures above 65 MPa. The T vs. P phase diagram exhibits the existence of a triple point (65 MPa, 207.6°C) for the cubic phase, a new mesophase (X), and the SmA phase, indicating the upper limit for the cubic phase. The new mesophase, denoted here as X, appears in place of the cubic phase at pressures above 65 MPa. The phase diagram also indicates that the Cr₄-Cr₃, Cr₃-Cr₂, and Cr₂-Cr₁ transition lines merge at about 40-50 MPa and then only the Cr₄-Cr₁ transition is observed in the solid state at higher pressures. Thus the phase transition process on heating changes from the sequence Cr₄-Cr₃-Cr₂-Cr₁-SmC-Cub-SmA-I₁-I₂ at atmospheric pressure to Cr₄-Cr₁-SmC-X-SmA-I₁-I₂ in the high pressure region above 65 MPa, via Cr₄-Cr₃-Cr₂-Cr₁-SmC-(X)-Cub-SmA-I₁-I₂ in the low pressure region.     

Thermal behaviour of the thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) under hydrostatic pressure

The phase behaviour of 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using high pressure differential thermal analysis. The phase transition sequence crystal 4 (Cr4)-crystal 3 (Cr3)-crystal 2 (Cr₂)-crystal 1 (Cr₁)-smectic C (SmC)-Cubic (Cub)-smectic A (SmA)-'structured liquid' (I₁)-isotropic liquid (I₂) was observed for a virgin sample on heating at atmospheric pressure. The stable temperature region of the optically isotropic cubic phase becomes narrower on increasing pressure and disappears at pressures above 65 MPa. The T vs. P phase diagram exhibits the existence of a triple point (65 MPa, 207.6°C) for the cubic phase, a new mesophase (X), and the SmA phase, indicating the upper limit for the cubic phase. The new mesophase, denoted here as X, appears in place of the cubic phase at pressures above 65 MPa. The phase diagram also indicates that the Cr₄-Cr₃, Cr₃-Cr₂, and Cr₂-Cr₁ transition lines merge at about 40-50 MPa and then only the Cr₄-Cr₁ transition is observed in the solid state at higher pressures. Thus the phase transition process on heating changes from the sequence Cr₄-Cr₃-Cr₂-Cr₁-SmC-Cub-SmA-I₁-I₂ at atmospheric pressure to Cr₄-Cr₁-SmC-X-SmA-I₁-I₂ in the high pressure region above 65 MPa, via Cr₄-Cr₃-Cr₂-Cr₁-SmC-(X)-Cub-SmA-I₁-I₂ in the low pressure region.     

Phase behavior of a thermotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitro- biphenyl-4-carboxylic acid under pressure

The phase behavior of an optically isotropic cubic mesogen 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid (ANBC-16) was investigated under hydrostatic pressures up to 200 MPa using a high-pressure DTA, a polarizing optical microscope equipped with a high-pressure hot-stage and a wide-angle X-ray diffractometer equipped with a high-pressure vessel. In the T vs. P phase diagram constructed in the heating mode, a triple point exists at 54±1 MPa and 205±1°C for the SmC, cubic, and SmA phases. A new mesophase, denoted here as X, appears in place of the cubic phase under pressures above about 60 MPa, while the X phase appears on cooling in the whole pressure region studied. Thus the X phase is a monotropic (metastable) phase between the SmA and Cub phases in the low pressure region, while being an enantiotropic phase between the SmA and SmC phases in the high pressure range. The X phase exhibits broken-fan or sand-like textures under pressure and a spot-like diffraction pattern, indicating the birefringent feature and no layered structure. It is suggested that the X phase is tetragonal or hexagonal columnar phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

Phase behaviour of the discotic mesogen 5,10,15,20-tetrakis (4-n-dodecylphenyl)porphyrin under pressure

The phase behaviour of the discotic mesogen 5,10,15,20-tetrakis(4-n -dodecylphenyl)porphyrin (C12TPP) was investigated under hydrostatic pressures up to 300MPa by high pressure DTA and wide angle X-ray diffraction methods. The typical enantiotropic phase transitions of C12TPP, low- to high-temperature crystal (Cr2-Cr1), Cr1-discotic lamellar phase (DL), and DL-isotropic liquid (I) are observed at pressures up to 10MPa. Application of hydrostatic pressure to the sample generates a pressure-induced crystal polymorph (Cr3) between the Cr2 and Cr1 phases, and the phase transitions Cr2-Cr3-Cr1-DL-I occur reversibly in the pressure region between 10 and 180MPa. On heating at higher pressures above 180MPa, the fourth crystal polymorph (Cr4) is formed between the Cr2 and Cr3 phases at lower temperatures, and at the same time the fifth crystal polymorph (Cr5) appears abruptly between the Cr1 and DL phases at high temperatures. The Cr2-Cr4-Cr3-C1-(Cr5)-DL-I transition processes were observed at 180 200MPa. Further increasing the pressure above 270MPa induces entirely different thermal behaviour: only two peaks for the pressure-induced transition between the sixth and fifth polymorphs (Cr6-Cr5) and the Cr5-I transitions are detected at low and high temperatures on heating, while both the DTA and WAXD experiments on cooling show the formation of the DL phase as a monotropic phase between the I and Cr5 phases, indicating the I DL Cr5 Cr6 process. The thermal behaviour was ambiguous and complex in the pressure region between 200 and 260MPa because the peaks for the intermediate crystal transitions were too small to detect with confidence. The two different sequences of the Cr2-Cr4-Cr3-Cr1-DL-I and Cr6-Cr5-(DL)-I processes seems to occur competitively. The T vs. P phase diagram of a sample cooled at 300MPa was studied to determine the triple point of the DL phase and to investigate the phase stability of the pressure-induced crystal polymorphs. The Cr6-Cr5-I transition process was observed on heating at 200 and 300MPa, while the Cr6-Cr5-DL-I process was detected at lower pressures below 100MPa. Since the Cr5-DL transition temperature changes linearly with a slope dT/dP 40 degrees C/100 MPa, while the DL-I transition temperature changes slightly (dT/dP 5.5 degrees C/100MPa), the DL phase forms a triangle in the T vs. P diagram. The triple point of the DL phase was found to be 240.8MPa and 168.8 C. The Cr6 polymorph reorganized to the stable Cr2 form under atmospheric pressure on annealing at room temperature overnight.     

Phase behaviour of the discotic mesogen 5,10,15,20-tetrakis (4-n-dodecylphenyl)porphyrin under pressure

The phase behaviour of the discotic mesogen 5,10,15,20-tetrakis(4-n -dodecylphenyl)porphyrin (C12TPP) was investigated under hydrostatic pressures up to 300MPa by high pressure DTA and wide angle X-ray diffraction methods. The typical enantiotropic phase transitions of C12TPP, low- to high-temperature crystal (Cr2-Cr1), Cr1-discotic lamellar phase (DL), and DL-isotropic liquid (I) are observed at pressures up to 10MPa. Application of hydrostatic pressure to the sample generates a pressure-induced crystal polymorph (Cr3) between the Cr2 and Cr1 phases, and the phase transitions Cr2-Cr3-Cr1-DL-I occur reversibly in the pressure region between 10 and 180MPa. On heating at higher pressures above 180MPa, the fourth crystal polymorph (Cr4) is formed between the Cr2 and Cr3 phases at lower temperatures, and at the same time the fifth crystal polymorph (Cr5) appears abruptly between the Cr1 and DL phases at high temperatures. The Cr2-Cr4-Cr3-C1-(Cr5)-DL-I transition processes were observed at 180 200MPa. Further increasing the pressure above 270MPa induces entirely different thermal behaviour: only two peaks for the pressure-induced transition between the sixth and fifth polymorphs (Cr6-Cr5) and the Cr5-I transitions are detected at low and high temperatures on heating, while both the DTA and WAXD experiments on cooling show the formation of the DL phase as a monotropic phase between the I and Cr5 phases, indicating the I DL Cr5 Cr6 process. The thermal behaviour was ambiguous and complex in the pressure region between 200 and 260MPa because the peaks for the intermediate crystal transitions were too small to detect with confidence. The two different sequences of the Cr2-Cr4-Cr3-Cr1-DL-I and Cr6-Cr5-(DL)-I processes seems to occur competitively. The T vs. P phase diagram of a sample cooled at 300MPa was studied to determine the triple point of the DL phase and to investigate the phase stability of the pressure-induced crystal polymorphs. The Cr6-Cr5-I transition process was observed on heating at 200 and 300MPa, while the Cr6-Cr5-DL-I process was detected at lower pressures below 100MPa. Since the Cr5-DL transition temperature changes linearly with a slope dT/dP 40 degrees C/100 MPa, while the DL-I transition temperature changes slightly (dT/dP 5.5 degrees C/100MPa), the DL phase forms a triangle in the T vs. P diagram. The triple point of the DL phase was found to be 240.8MPa and 168.8 C. The Cr6 polymorph reorganized to the stable Cr2 form under atmospheric pressure on annealing at room temperature overnight.     

Phase behaviour of the discotic mesogen 2,3,6,7,10,11-hexahexylthiotriphenylene (HHTT) under hydrostatic pressure

The phase behaviour of the discotic mesogen 2,3,6,7,10,11-hexahexylthiotriphenylene (HHTT) was investigated under hydrostatic pressures up to 500 MPa using high pressure optical and DTA measurements. The known enantiotropic phase transitions of HHTT, i.e. crystal (Cr)-helical phase (H), H-hexagonal columnar phase (Col_h) and Col_h-isotropic liquid (I) were observed up to 32 MPa. Application of hydrostatic pressures above 32 MPa results in the H and Col_h phases becoming monotropic, depending upon the applied pressure. The H phase was observed as a monotropic phase in the pressure region between 32 and about 180 MPa. Thus, the I →Col_h →H →Cr transition sequence appeared only on cooling under these pressures, while the Cr →Col_h →I transition occurred on heating. Further increases in pressure above a second limiting value leads to the Col_h phase becoming monotropic. Thus the I →Col_h →Cr transition sequence appeared on cooling, while the Cr →I transition was observed on heating. The T vs. P phase diagram based on the data obtained in the heating mode contains two triple points; one is estimated as 40 MPa, 77.2°C for the Cr-H-Col_h triple point and the other is extrapolated as 285 MPa, 118.3°C for the Cr-Col_h-I triple point. These triple points define the upper limits for the appearance of the stable H and Col_h phases, respectively.     

Phase behaviour of thermotropic banana-shaped compounds under pressure

The phase behaviour of two achiral bent core banana-shaped compounds, the hexyloxy (compound I) and decyloxy (compound II) members of the 1,3-phenylene bis[N-(2-hydroxy-4-n-alkoxybenzylidene)-4'-aminobenzoate] series was investigated under hydrostatic pressures up to 300 MPa using high pressure differential thermal analysis and light transmission methods. The reversible transition sequence crystal (Cr₁)-B₁ phase-isotropic liquid (I), observed at room pressure for compound I, remains in the pressure region up to c 70 MPa. At higher pressures a pressure-induced crystalline phase (Cr_i) appears between the Cr₁ and B₁ phases, its temperature region becoming wider with increasing pressure. The temperature vs. pressure phase diagram shows a triple point of 72.9 MPa and 160.3°C for the Cr₁, Cr_i and B₁ phases, indicating the lower limit of pressure for the Cr_i phase. In compound II the reversible transition sequence crystal (Cr₁)-B₂ phase-I is seen over the whole pressure region, and the temperature range of the B₂ phase remains unaltered. It is concluded that both the B₁ and B₂ banana phases are stable over the whole pressure region studied.     

Phase behaviour of thermotropic banana-shaped compounds under pressure

The phase behaviour of two achiral bent core banana-shaped compounds, the hexyloxy (compound I) and decyloxy (compound II) members of the 1,3-phenylene bis[N-(2-hydroxy-4-n-alkoxybenzylidene)-4′-aminobenzoate] series was investigated under hydrostatic pressures up to 300?MPa using high pressure differential thermal analysis and light transmission methods. The reversible transition sequence crystal (Cr₁)–B₁ phase–isotropic liquid (I), observed at room pressure for compound I, remains in the pressure region up to c 70?MPa. At higher pressures a pressure-induced crystalline phase (Cr_i) appears between the Cr₁ and B₁ phases, its temperature region becoming wider with increasing pressure. The temperature vs. pressure phase diagram shows a triple point of 72.9?MPa and 160.3°C for the Cr₁, Cr_i and B₁ phases, indicating the lower limit of pressure for the Cr_i phase. In compound II the reversible transition sequence crystal (Cr₁)–B₂ phase–I is seen over the whole pressure region, and the temperature range of the B₂ phase remains unaltered. It is concluded that both the B₁ and B₂ banana phases are stable over the whole pressure region studied.     

Coexistence of two aggregation modes in exotic liquid-crystalline superstructure: systematic maximum entropy analysis for cubic mesogen, 1,2-bis(4'-n-alkoxybenzoyl)hydrazine [BABH(n)

Structure of a complex superstructure self-organized by thermotropic mesogen, 1,2-bis(4'- n-alkoxybenzoyl)hydrazine [BABH(n), where n is the number of carbon atoms in an alkoxy chain] was studied while paying special attention to the structure at the molecular level. Maximum entropy (MEM) analysis revealed that the molecular cores form two kinds of aggregates: Jungle gym with 3-fold junctions roughly on P minimal surface and spherical shells.     

Calorimetric study on the thermotropic cubic mesogen, 4'-n-hexadecyloxy-3'-nitrobiphenyl-4-carboxylic acid, ANBC(16)

The heat capacity of ANBC(16) has been measured between 15 and 500 K by adiabatic calorimetry. Three (one known and two newly found) crystal-crystal phase transitions and all the known liquid crystalline phases (SmC, cubic D and SmA) were detected. The temperatures, enthalpies and entropies of transition were determined for all the phase transitions observed. The entropy of transition is very small for the transition from/to the cubic D mesophase. The results are compared with the thermal properties of another cubic mesogen, BABH(8). The logical possibility is pointed out that the cubic mesophases of ANBC(16) and BABH(8) are of identical higher order structure, while discussing the fact that they are immiscible.     

Crystal structure of 1,2-bis-(phenylseleno)-1,2-dichlorethene

Vladimir State Pedagogical Institute. Institute for Elementorganic Compounds, Russian Academy of Sciences. Irkutsk Institute for Organic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 4, pp. 153–154, July–August, 1992.     

Thermodynamic functions of thermotropic polyethers based on the semiflexible mesogen 1-(4-hydroxyphenyl)-2-(2-methyl-4-hydroxyphenyl)ethane

Heat capacities of a series of thermotropic polyethers consisting of a semiflexible mesogen [1-(4-hydroxyphenyl) - 2 - (2 - methyl - 4 - hydroxyphenyl)ethane], with n methylene flexible spacers (n = 4–12) (MBPE-n) have been measured by DSC and fitted at low temperature to an approximate frequency spectrum, as well as at high temperature to a general equation for the liquid MBPE-n. The latter equation is: C_p = n(17.33 + 0.04551T) + (280.9 + 0.3839T) where n is the number of methylenes in the polyether spacer. The calculated vibration-only heat capacities start to show deviations from the measured heat capacities below the melting temperature, reflecting contributions from conformational disorder and motion in methylene spacers. It is suggested that part of this increase in heat capacity can be looked upon as a glass transition of the partially conformationally disordered crystals. Solid state ¹³C–NMR studies showed similarly that over the range of temperature some of the C? C bonds in the spacer are in a rotational state similar to that in the melt. The equilibrium heats of fusion (ΔH) and the changes of heat capacity (ΔC_p) for the amorphous polymer at the glass transition temperature, T_g, were determined by WAXD and DSC. Based on the discrepancy of ΔC_p it is concluded that these phenylene containing polyethers have a certain amount of rigid amorphous polymer. Thermodynamic functions H, S and G for all of the polyethers have been established.     

Pressure-scanning DTA measurements of the cubic-smectic C phase transition of 1,2-bis-(4-n-octyloxy)- and 1,2-bis-(4-n-dodecyloxy benzoyl)hydrazines

The pressure-scanning differential thermal analyzer (DTA) measurements of the cubic (Cub)-smectic C (SmC) transition of thermotropic cubic mesogens of 1,2-bis-(4-n-octyloxybenzoyl)- and 1,2-bis-(4-n-dodecyloxybenzoyl)hydrazine, BABH(8) and BABH(12), were performed at isothermal condition using a high-pressure differential thermal analyzer. BABH(8) showed the same endothermic peak of the Cub-SmC transition in the pressurizing process as on heating at isobaric condition. On the other hand, BABH(12) showed only the cubic phase between the crystal and the isotropic liquid under pressures up to 16-17 MPa, but a high-pressure smectic C (SmC(hp)) phase was induced instead of the cubic phase under higher pressure. The Cub-SmC(hp) phase transition with a small exothermic peak occurred in the pressurizing process and the transition was observed reversibly. The Cub-SmC(hp) phase transition was in accordance with the morphological and structural observations mentioned before. The strange phenomenon of the inversion of sign of the Cub-SmC transition heat of BABH(n) homologues can be explained by the “Alkyl-chains as entropy reservoir” mechanism proposed by Saito et al.     

Calorimetric study of the cubic mesogen, ACBC(6)

The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500 K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165 K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30 K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC-cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic-isotropic liquid phase transition.     

Calorimetric study of the cubic mesogen,ACBC(16)

The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500?K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165?K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30?K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC–cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic–isotropic liquid phase transition.