Synthesis and mesomorphic properties of chiral liquid crystals having thiolactate groups

A homologous series of chiral thiolactate liquid crystals, alkyl 2-[4-(4-decyloxyphenyl)benzoyloxyphenyloxy]thiopropionates, ADBPT-n (n=2-6), was prepared from (R)-2-(4-hydroxyphenoxy)propionic acid. Structural effects on the mesomorphic and physical properties were investigated in terms of variation in the length of alkyl chain attached to the thiolactate group. The mesophases and their corresponding transition temperatures were identified by polarizing optical microscopy and differential scanning calorimetry. Compound ADBPT-4 exhibited SmA* and SmC* phases, whereas other compounds in the series exhibited the SmA* phase along with unidentified SmX₁* and SmX₂* phases. The maximum P_s value measured for ADBPT-4 in the SmC* phase was 17.5 nC cm^-2, suggesting the polarization of the material is rather low. The tilt angles were also measured, reaching a maximum of 48 degree.     

Synthesis and characterization of a novel liquid crystal series with tribenzoate cores and monofluoro-substitution on the phenyl ring near the chiral chain

Two new chiral series, with benzoate cores and monofluoro-substitution in positions 2 and 3 of the first phenyl ring near the chiral chain, have been synthesized and characterized. The mesomorphic properties have been analysed by optical microscopy, differential scanning calorimetry and electro-optical measurements. The first series (I_c) displays a very rich polymorphism including SmA, SmC*_α, SmC*, SmC*_FI, SmC*_A phases, whereas the second (I_b) does not exhibit the SmC*_A phase, and moreover only displays the SmA phase for short alkoxy chains. The effect of the position of the fluoro substituent and the influence of the alkoxy chain length on the mesomorphic behaviour are discussed.     

The effect of the alkyl chain length on the mesomorphic properties of new lactic acid derivatives

New series of lactic acid derivatives with alkyl terminal chain have been synthesised and their mesomorphic properties studied. We have varied the length of chiral and non-chiral terminal alkyl chains and found that prolonging both chains has a strong effect on the SmA*–SmC* phase transition. Most of the new materials exhibit only paraelectric SmA* phase; for homologues with a longer non-chiral chain (m ≥ 10), the ferroelectric (SmC*) phase appears below the SmA* on cooling and persists down to a room temperature. The role of the chiral terminal chain in the molecule is quite opposite – only its short length supports the existence of ferroelectric phase. Additionally, a hexatic phase appeared below the SmA*–SmC* phase sequence for several homologues at low temperatures. All materials have been studied using standard experimental techniques (differential scanning calorimetry (DSC), texture observations, polarisation and tilt angle measurements, etc.). Liquid crystalline properties of new materials have been compared with the previously prepared and studied lactic acid derivatives.     

Novel ferroelectric liquid crystals based on fused thieno[3,2-b]furan and thieno[3,2-b]thiophene cores

Several series of new benzofused thieno[3,2-b]furan- and thieno[3,2-b]thiophene-based derivatives have been synthesized and their mesomorphic properties investigated. All the studied compounds exhibit a SmC* phase with very wide temperature interval. Additionally, some types of the compounds show the cholesteric, SmA or blue phase. In the ferroelectric SmC* phase we evaluated physical properties of relevance for possible applications.     

Synthesis and mesomorphic properties of liquid crystalline [1]benzothieno[3,2-b][1]benzothiophene derivatives

Two new series of chiral aliphatic and aromatic esters of 7-decyl[1]benzothieno[3,2-b][1]benzothiophene-2-carboxylic acid were synthesized and their mesomorphic behaviour studied. While the chiral aliphatic esters exhibited only the SmA phase, the antiferroelectric SmC_A* phase was found for esters with chiral 4-hydroxybenzoates; for one homologue a ferroelectric SmC* phase was also observed. Introduction of lateral substituents in the 3-position of the 4-hydroxybenzoic acids (methoxy, fluoro, chloro, and bromo) led to a reduction of the polymorphism and only the SmA phase remained.     

Synthesis,properties and crystal structure of chiral semiperfluorinated liquid crystals with ferro and anticlinic smectic phases

A new chiral and semiperfluorinated series with ferro and anticlinic properties has been synthesized and characterized. The mesomorphic behaviour has been established on the grounds of both microscopic observations and DSC measurements. The non-chiral intermediate ethyl 4-semiperfluorinated alkyloxybenzoates exhibit SmA phases, unusual for compounds with a single phenyl ring. The final derivatives display SmA, SmC* and in several cases SmC*A phases. The longer fluorinated chains favour the SmA and SmC* phases at the expense of the SmC*A phase. Electro-optical measurements were carried out with the classical SSFLC geometry. The spontaneous polarization and tilt angle at saturation are higher than those of the hydrogenous homologues, around 140 nCcm-2 at 40 degrees C. One compound of the series, the 4,4,5,5,6,6,7,7,8,8,8-nonafluoroheptyloxy derivative, C36H35O7F9, Mx=750.6 g mol-1, crystallizes in the triclinic system, space group P1 with four independent molecules in the asymmetric unit (Z=4). The molecules are arranged in a head-to-tail fashion with two molecules oriented in the same direction and the two others in the opposite direction. They give rise to sheets with a smectic C-like arrangement. The final reliability factors were R=0.117 and wR=0.134; the goodness of fit was S=1.366.     

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.     

Synthesis, properties and crystal structure of chiral semiperfluorinated liquid crystals with ferro and anticlinic smectic phases

A new chiral and semiperfluorinated series with ferro and anticlinic properties has been synthesized and characterized. The mesomorphic behaviour has been established on the grounds of both microscopic observations and DSC measurements. The non-chiral intermediate ethyl 4-semiperfluorinated alkyloxybenzoates exhibit SmA phases, unusual for compounds with a single phenyl ring. The final derivatives display SmA, SmC* and in several cases SmC*A phases. The longer fluorinated chains favour the SmA and SmC* phases at the expense of the SmC*A phase. Electro-optical measurements were carried out with the classical SSFLC geometry. The spontaneous polarization and tilt angle at saturation are higher than those of the hydrogenous homologues, around 140 nCcm-2 at 40 degrees C. One compound of the series, the 4,4,5,5,6,6,7,7,8,8,8-nonafluoroheptyloxy derivative, C36H35O7F9, Mx=750.6 g mol-1, crystallizes in the triclinic system, space group P1 with four independent molecules in the asymmetric unit (Z=4). The molecules are arranged in a head-to-tail fashion with two molecules oriented in the same direction and the two others in the opposite direction. They give rise to sheets with a smectic C-like arrangement. The final reliability factors were R=0.117 and wR=0.134; the goodness of fit was S=1.366.     

Novel ferroelectric liquid crystals based on fused thieno[3,2‐b]furan and thieno[3,2‐b]thiophene cores

Several series of new benzofused thieno[3,2‐b]furan‐ and thieno[3,2‐b]thiophene‐based derivatives have been synthesized and their mesomorphic properties investigated. All the studied compounds exhibit a SmC* phase with very wide temperature interval. Additionally, some types of the compounds show the cholesteric, SmA or blue phase. In the ferroelectric SmC* phase we evaluated physical properties of relevance for possible applications.     

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°.     

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*_β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*_α, SmC*_β, SmC*_γ and SmC*_a. We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA* -SmC*_a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*_β and SmC*_γ have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved.     

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 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.     

Synthesis and mesomorphic properties of a new chiral series with a heterocycle in the molecular core

We report a number of different homologous series with a heterocycle incorporated in the molecular core near the chiral chain. Two of these series differ in the type of chiral chain, -CH*(CH 3 )C 6 H 13 or -CH*(CH 3 )-CO 2 -C 4 H 9 . Their properties are compared and found to show completely different polymorphism. The first series exhibits only SmC* and SmA phases whereas the second possesses TGB, N* and BP phases. The mesomorphic properties were studied by optical microscopy, DSC and electro-optical measurements. The effect of substitution of the phenyl ring near the chiral chain by a heterocycle is discussed.     

Chiral Liquid Crystals Synthesized from 2(S)‐[2(R)‐Methylhexyloxy]Propanol and its (S,S)‐Diastereomer

Two new chiral alcohols, 2(S)‐[2(R)‐methylhexyloxy]propanol ( 5 ) and 2(S)‐[2(S)‐methylhexyloxy]propanol ( 6 ), were prepared from the corresponding propionic acid ethyl ester 1 and 2 in the presence of sodium borohydride. They were used as the chiral moiety for the synthesis of two diastereomeric liquid crystals 7 and 8 . Both of them exhibit the phase sequence I‐SmA‐SmC*‐SmX‐Cr. The mesogenic properties of the (S,S)‐diastereomer 8 are more unique in comparison with those of the (S,R)‐diastereomer 7. It possesses not only lower SmA and SmC* phase transition temperature, 103 °C vs. 112 °C for SmA phase and 31 °C vs. 65 °C for SmC* phase, but wider SmA and SmC* phase range, 40 °C vs. 31 °C for SmA phase and 72 °C vs. 47 °C for SmC* phase. The diastereomer 8 also has a larger Ps value than that of 7, 24 vs. 15 nC cm^?2 measured at Tc ‐ T = 10 °C. The difference in these mesogenic properties is discussed by comparing their conformation difference at the molecular part of benzoate.     

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.     

Oxadiazole-based unsymmetrical chiral liquid crystal dimers: synthesis and mesomorphic properties

The synthesis and liquid crystalline properties of novel chiral Schiff's base dimers containing the 1,3,4-oxadiazole ring are reported. The length of the terminal S-alkyl chain has been varied. All the compounds synthesised were thermally stable and exhibited enantiotropic mesomorphism, showing either SmC*–SmA–TGB–N*–BP or SmC*–SmA phase sequence.     

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.     

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.     

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.