Synthesis and ferroelectric properties of chiral swallow-tailed liquid crystals derived from (S)-2-[1-(2-ethylbutoxy)]propanol

(S)-2-[1-(2-Ethylbutoxy)]propanol was designed and synthesized as a chiral building block for the preparation of chiral liquid crystals. Its derivatives, the (S)-2-[1-(2-ethylbutoxy)]propyl 4-[4-(4-alkoxyphenyl)phenoyloxy]benzoates, EPmPPB (m = 8-12), were prepared and their mesomorphic phases investigated. The results showed that the chiral materials displayed enantiotropic SmA* and SmC* phases, while those with shorter alkyl chains (m = 8-10) displayed an additional unidentified SmX* phase. The switching current, spontaneous polarization, tilt angle, dielectric constant and electro-optical response for the materials in the ferroelectric SmC* phase were measured. The electro-optic responses of the materials in polyimide film-coated, homogeneously aligned cell exhibit thresholdless, V-shaped switching in the ferroelectric phase.     

Synthesis and ferroelectric properties of chiral liquid crystals derived from (S)-1-propyloxy-2-propanol

A new optically active chiral moiety, (S)-1-propyloxy-2-propanol, was designed and synthesized by the treatment of 1-propanol with (S)-propylene oxide under basic conditions. Its derivatives, the (R)-1-propyloxy-2-propyl 4-[4-(4-alkoxyphenyl)phenoyloxy]benzoates, PPmPPB (m = 8-12), were prepared for the investigation of mesomorphic properties. All of the chiral materials displayed enantiotropic SmA* and SmC* phases, and the shorter alkyl chain members (m = 8-11) displayed an additional unidentified SmX* phase. The switching current, spontaneous polarization, tilt angle, dielectric constant and electro-optical response for the materials in the ferroelectric SmC* phase were measured. The electro-optic responses in polyimide film-coated homogeneously aligned cells exhibit thresholdless, V-shaped switching in the ferroelectric phase.     

Synthesis and mesomorphic properties of chiral liquid crystals derived from ( S )-lactic acid with 3-pentanol

The chiral swallow-tailed liquid crystals, 1-ethylpropyl (R)-2-[4-(4′-alkoxybiphenylcarbonyloxy)-phenoxy]propionates, EPmPBPP (m = 8?12), were prepared by using chiral (S)-lactic acid with 3-pentanol as starting materials. Mesophases and their corresponding transition temperatures were determined by polarizing microscopic textures and DSC. The results showed that all the chiral materials exhibited enantiotropic BP, N*, TGBA*, SmA*, and SmC* phases. Spontaneous polarization, dielectric constant and electro-optical response for the materials in the ferroelectric SmC* phase were investigated. It was noted that the electro-optical response of transmittance versus applied voltage obtained from the ferroelectric phase of material EPmPBPP (m = 10) displayed V-shaped switching, while that of other materials displayed the typical characteristics of ferroelectric hysteresis switching or U-shaped switching.     

Ferroelectric liquid crystals with a thioester linking group positioned at the chiral tail

A homologous series of chiral thioesters, hexyl (2S)-2-[6-(4-alkanoyloxyphenyl)benzoyloxy-2'-naphthyl]thiopropionates, HnPBNTP (n=7-11) was synthesized, and the mesophases and electro-optical properties were studied. All the materials possess a ferroelectric SmC* phase, which was confirmed by the switching current behaviour. It was found that compounds with a shorter alkyl chain length (n=7-9) displayed SmA* and SmC* phases, while, compounds with a longer alkyl chain length (n=10 and 11), displayed the SmC* phase exclusively. Spontaneous polarization and apparent tilt angle were also measured. The maximum P_s values are in the range 15-26 nC cm^-2, and the maximum θ values are in the range 23°-28°.     

Synthesis and mesomorphic properties of fluoro-substituted chiral liquid crystals derived from (S)-lactic acid with alkoxyethanols

A homologous series of fluoro-substituted chiral liquid crystals derived from (S)-lactic acid and alkoxyethanols were prepared for investigation. Mesophases and their corresponding transition temperatures were identified by polarized optical microscopy and differential scanning calorimetry. The compounds exhibit a broad temperature range in the ferroelectric chiral smectic C (SmC*) phase; in particular, compounds with shorter alkyl chain lengths have an SmC* phase at ambient temperature. The physical properties of the ferroelectric SmC* phase, such as switching current, spontaneous polarization, optical tilt angle and electro-optical response, were also measured. The effects of fluoro substituent on the mesophases and physical properties of the chiral liquid crystals are discussed.     

Synthesis and ferroelectric properties of new chiral liquid crystals derived from (S)-lactic acid with alkoxyethanols

A homologous series of chiral materials derived from (S)-lactic acid with alkoxyethanols has been synthesized and their mesomorphic properties investigated. The mesophases and their corresponding transition temperatures were identified by differential scanning calorimetry and polarizing optical microscopy. The spontaneous polarization and electro-optical response of ferroelectric SmC* phase are measured and reported.     

V-shaped switching in binary mixtures of an achiral swallow-tailed material with the antiferroelectric liquid crystal (S)-MHPOBC

An achiral swallow-tailed material, 2-propylpentyl 4-(4'-decyloxybiphenyl-4-carbonyloxy)benzoate, p, showing SmA and SmC_alt phases was prepared for mixing (by weight percentage) with an antiferroelectric liquid crystal, (S)-MHPOBC, m, for the study. The binary mixture p15/m85 using (S)-MHPOBC (85%) as a host doped with achiral material (15%) resulted in a phase sequence SmA-SmC*-SmC*_A. The electro-optic response of this mixture in the ferroelectric SmC* phase displayed V-shaped switching, while that in the antiferroelectric SmC*_A phase displayed a double hysteresis switching. The mixture p85/m15 possessed SmA* and SmC*_A phases; V-shaped switching was found in the antiferroelectric SmC*_A phase of this mixture. These optical phenomena implied that a binary mixture containing a larger amount of achiral swallow-tailed material and/or possessing relatively lower polarization favours the occurrence of V-shaped switching in the antiferroelectric phase. The results of this work also suggested that thresholdless V-shaped switching in chiral smectic liquid crystals can be achieved by mixing an achiral swallow-tailed material with an antiferroelectric liquid crystal.     

Synthesis and mesomorphic properties of chiral swallow-tailed thioester liquid crystals with lateral substituents

Two homologous series of chiral swallow-tailed thioester materials, 1-ethylpropyl (R)-2-[3-fluoro-4-(4'-alkyloxybiphenylcarbonylthio)phenoxy]propionates, I-6 (m = 8-12), and 1-ethylpropyl (R)-2-[3-methyl-4-(4'-alkyloxybiphenylcarbonylthio)phenoxy]propionates, II-6 (m = 8-12), have been synthesized and their mesomorphic phases studied. The results show that materials I-6 (m = 8-12) with a fluoro substituent, display the phase sequence I-BPII-N*-SmC*-Cr, whereas materials II-6 (m = 8-12) with a methyl substituent display the phase sequence I-N*-TGBA*-SmA*-Cr during cooling. The physical properties of the SmC* phase in materials I-6 were measured. The results show that the maximum P _s values are in the range 91-95 nC cm^-2 and the maximum tilt angles are about 34-37°.     

Chiral two ring compounds exhibiting antiferroelectric phases

Novel chiral two ring compounds possessing phenylethenoate moieties were synthesized and their liquid crystalline properties determined. Some of these compounds were found to exhibit SmC* γ, AF and SmC* A phases, whereas in other compounds only SmA* and SmC* phases appear. The influence of the molecular structure on the appearance of SmC* γ, AF and SmC* γ phases is discussed. The basic electro-optical properties of the homologous series of ( S )-( E )4-(1-methylheptyloxycarbonyl)phenyl 4-alkoxycinnamates, in which SmC*, SmC* γ, AF and SmC* A phases appear, were also investigated. High values of spontaneous polarization, low threshold voltages and fast switching times at room temperature were observed.     

New antiferroelectric liquid crystalline materials containing a keto group and two lactate groups

New chiral liquid crystalline materials containing a keto group and two lactate units attached to the mesogenic core have been synthesized and studied. All the new compounds show the paraelectric SmA, ferroelectric SmC* and antiferroelectric SmC*_A phases each over rather broad temperature ranges. The properties of the phases were characterized by DSC, electro-optical and dielectric studies. The spontaneous polarization, tilt angle, helical pitch, and switching times were determined for the polar phases.     

V-shaped switching in binary mixtures of an achiral swallow-tailed material with the antiferroelectric liquid crystal (S)-MHPOBC

An achiral swallow-tailed material, 2-propylpentyl 4-(4′-decyloxybiphenyl-4-carbonyloxy)benzoate, p, showing SmA and SmC_alt phases was prepared for mixing (by weight percentage) with an antiferroelectric liquid crystal, (S)-MHPOBC, m, for the study. The binary mixture p/15/m85 using (S)-MHPOBC (85%) as a host doped with achiral material (15%) resulted in a phase sequence SmA-SmC*-SmC*_A. The electro-optic response of this mixture in the ferroelectric SmC* phase displayed V-shaped switching, while that in the antiferroelectric SmC*_A phase displayed a double hysteresis switching. The mixture p85/m15 possessed SmA* and SmC*_A phases; V-shaped switching was found in the antiferroelectric SmC*_A phase of this mixture. These optical phenomena implied that a binary mixture containing a larger amount of achiral swallow-tailed material and/or possessing relatively lower polarization favours the occurrence of V-shaped switching in the antiferroelectric phase. The results of this work also suggested that thresholdless V-shaped switching in chiral smectic liquid crystals can be achieved by mixing an achiral swallow-tailed material with an antiferroelectric liquid crystal.     

Direct transition from the SmA phase to the tilted hexatic phase in liquid crystals with several lactate units

Compounds with differing numbers of lactate units in the chiral part were synthesized. For all materials, at least two smectic phases were found. In addition to the SmA, the SmC* and/or the tilted hexatic SmI*(F*) phase appear according to the length of the non-chiral alkyl chain. For the shortest non-chiral chain, a direct transition from the SmA phase to the SmI*(F*) phase has been discovered and studied. For compounds with the 2-(S)-methylbutyl alkyl chain and two lactate units in the chiral part the antiferroelectric SmC*_A phase occurs. The ferroelectric character of the hexatic phase has been confirmed even just below the SmC*_A phase.     

Synthesis and mesomorphic properties of chiral liquid crystals derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid with a methyleneoxy linking group

Three homologous series of chiral materials derived from (S)-2-(6-hydroxy-2-naphthly)propionic acid with a methyleneoxy linking group were synthesized for the investigation of mesomorphic properties. All the materials displayed enantiotropic SmA* and SmC* phases. The spontaneous polarization (P _s) and optical tilt angles in the SmC* phase of the chiral materials were measured. The maximum spontaneous polarizations are in the range 12.3-19.1 nC cm^-2. No significant difference could be found in the P _s values with respect to the various alkyl chiral chain lengths, n. The maximum optical tilt angles are in the range 25-30°. The optical tilt angles decrease with the increase in alkyl chain length, n.     

Ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid with non‐fluorinated or semi‐fluorinated alkanes at a chiral terminal chain

Two series of ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid, with non‐fluorinated or semi‐perfluorinated alkanes positioned at a chiral terminal chain, have been synthesized and characterized by differential scanning calorimetry, polarizing optical microscopy and electro‐optical measurements. The non‐fluorinated compounds, 1‐hexyl (S)‐2‐{6‐[4‐(4‐alkanoyloxyphenyl)benzoyloxy]‐2‐napthyl}propionates exhibit rich mesomorphism—the BP_II, N*, TGB_A*, SmA* and SmC* phases. The fluorinated compounds display only the SmA* and SmC* phases, suggesting that the fluorination promotes the formation of smectic phases. In addition, the SmA* and SmC* phases of the fluorinated compounds have enhanced thermal stability as compared with the corresponding phases of the non‐fluorinated compounds. The spontaneous polarization (P _s values) for the non‐fluorinated compounds are higher than those of the fluorinated compounds at any reduced temperature below the SmA*–SmC* transition. The electro‐optical responses measured for these compounds in the ferroelectric phase displayed thresholdless, V‐shaped switching.     

New antiferroelectric liquid crystalline materials containing a keto group and two lactate groups

New chiral liquid crystalline materials containing a keto group and two lactate units attached to the mesogenic core have been synthesized and studied. All the new compounds show the paraelectric SmA, ferroelectric SmC* and antiferroelectric SmC*_A phases each over rather broad temperature ranges. The properties of the phases were characterized by DSC, electro-optical and dielectric studies. The spontaneous polarization, tilt angle, helical pitch, and switching times were determined for the polar phases.     

Evidence of electroclinic effect in some TGBA mesophases

Two members of a chiral tolane series exhibiting a new TGBA phase and a S*_C ferroelectric phase have been investigated by means of electro-optical measurements. These materials belong to the optically active series of (R)-4-(1-methylheptyloxycarbonyl)-4'-(4'- alkyloxy-3'-fluorobenzoyloxy) tolanes and are the tetra- and octa-decyloxy derivatives. Due to the large pitch values in these TGBA mesophases, complete unwinding of the helix is found to be possible in thick cells. This also allows measurements of the electroclinic properties, such as the electric field induced tilt angle, response time, and the ferroelectric properties in the S*_C phase.     

Synthesis and ferroelectric properties of chiral swallow-tailed liquid crystals derived from (L)-lactic acid

Three homologous series of chiral swallow-tailed materials derived from (L)-lactic acid were prepared. Structural effects on the mesomorphic and physical properties were investigated in terms of (i) the variation of non-chiral peripheral length chain, (ii) the variation of swallow-tailed groups and straight alkyl chain at the chiral tails, and (iii) lateral halogen substituents in the core of the molecules. The mesophases and their corresponding transition temperatures were identified by optical polarized microscopy and differential scanning calorimetry. The physical properties of the ferroelectric SmC* phases such as switching current, spontaneous polarization and electro-optical response were also measured and compared.     

Synthesis and ferroelectric properties of chiral swallow-tailed liquid crystals derived from (L)-lactic acid

Three homologous series of chiral swallow-tailed materials derived from (L)-lactic acid were prepared. Structural effects on the mesomorphic and physical properties were investigated in terms of (i) the variation of non-chiral peripheral length chain, (ii) the variation of swallow-tailed groups and straight alkyl chain at the chiral tails, and (iii) lateral halogen substituents in the core of the molecules. The mesophases and their corresponding transition temperatures were identified by optical polarized microscopy and differential scanning calorimetry. The physical properties of the ferroelectric SmC * phases such as switching current, spontaneous polarization and electro-optical response were also measured and compared.     

Dynamics in ferro- and antiferroelectric phases of a liquid crystal with fluorinated molecules as studied by dielectric spectroscopy

For 1-[3-fluoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4-2,2,3,3,4,4,4-heptafluorobutoxybutoxy)biphenyl-4-yl]ethane (1F7), built of chiral molecules, results of dielectric measurements of liquid-crystalline and solid phases are presented. Rich polymorphism of liquid-crystalline (SmC*, SmC*_A and SmI*_A) phases as well as of solid (Cr1 and Cr2) phases were observed down to –130°C. At a frequency range from 0.1 Hz to 3 MHz, the relaxation processes were detected in ferroelectric SmC*, antiferroelectric SmC*_A and highly ordered SmI*_A smectic phases. The mechanism of complex dynamics (moleculear and collective) was identified with the help of the bias field. Vitrification of conformationally disordered crystal phase Cr2 was found in accordance with calorimetric observations.     

Synthesis and characterization of a chiral antiferroelectric series with new SmC A*-L transition

Two new chiral series with a tolane core: (S) 4-(1-methylheptyloxycarbonyl)phenyl (series IB) and (S) 4-(1-ethylheptyloxycarbonyl)phenyl (series IC) 4-alkanoyloxytolane-4'-carboxylates have been synthesized and characterized. All the compounds are mesomorphic, and most of them display the antiferroelectric SmC*A phase. The mesomorphic properties have been analysed by optical microscopy, DSC, helical pitch and electro-optical measurements and X-ray diffraction study. Series IB exhibits a very rich polymesomorphism with SmC*alpha, SmC*, SmC* F12, SmC* F11 and SmC*A phases, like the previously reported series IA, [(S) 4-(1-methylheptyloxycarbonyl)phenyl 4-alkyloxytolane-4-carboxylates]. Series IC is more interesting because it presents for the first time in antiferroelectric series the liquid-like phase (L phase) between the SmC*A and isotropic phases. Preliminary optical studies plead in favour of a helical short range structure for this new liquid-like L phase.