Mesomorphic properties of 5boSOMH from new three rings thiobenzoate series

Phase polymorphism of a novel chiral liquid crystalline compound (S)-(+)-4-{4-(4-n-pentylbicyclo[2,2,2]octancarbonylthio)benzoyloxy}benzoate 1-methylheptyl (in short: 5boSOMH) was examined with three complementary methods: Differential Scanning Calorimetry (DSC), Polarized Light Optical Microscopy (POM) and Transmitted Light Intensity (TLI). X-Ray diffraction was used to learn about molecular arrangement in ordered phases. 5boSOMH has two enantiotropic phases: SmB* and SmA*, and exhibits solid phase polymorphism.     

Induction of smectic layering in nematic liquid crystals using immiscible components IV. The effect of bulky lateral carboxyl substituents on the thermotropic behaviour of 2,5-bis[4-(n-perfluoroheptyloctyloxy)benzoyloxy]toluene

Bulky lateral carboxylate substituents were introduced at the benzylic position of 2,5-bis[4-(n-perfluoroheptyloctyloxy)benzoyloxy]toluene by esterification of the corresponding benzyl bromide with potassium carboxylates. In spite of the bulky lateral substituents, none of the 2,5-bis[4-(n-perfluoroheptyloctyloxy)benzoyloxy]benzyl carboxylates exhibit a nematic mesophase in addition to, or instead of, the smectic mesophases. All of the crystalline and SmC-SmA transition temperatures and, with the exception of the 9-anthracene carboxylate derivative, all of the isotropization temperatures of the resulting 2,5-bis[4-(n-perfluoroheptyloctyloxy)benzoyloxy]benzyl carboxylates are lower than those of the parent toluene compound. The SmC-SmA transition decreases the most, thereby stabilizing the SmA mesophase. In most cases, the SmC mesophase is destabilized from an enantiotropic to a monotropic mesophase. There is no correlation between any of the transition temperatures and the size of the lateral substituent.     

The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

The mesomorphic anomaly of 4-[2-(4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-pentylcyclohexyl-1-carboxylates

Four homologous series of 4-[2-[4-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] phenyl trans-4-alkylcyclohexyl-1-carboxylates have been prepared. Their liquid crystalline behaviour was investigated by optical polarizing microscopy and DSC. Series A, B and C exhibit the nematic phase. The phase transition behaviour of series D is anomalous. The compounds of series D with a short alkoxy chain exhibit enantiotropic smectic A and nematic phases, while those with a long alkoxy chain exhibit only the nematic phase.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Esters derived from 7-decanoyloxychromone-3-carboxylic acid: synthesis and mesomorphic properties

The synthesis and liquid crystalline properties of a new series of calamitic liquid crystals containing 4-H-benzopyran-4-one (chromone) within the central core is reported. The first homologue in the series display SmA phase (8a), the homologues (8b-e) exhibit SmA and SmC mesophases and the homologues (8f-h) exhibit only a SmC mesophase.     

Mesomorphic behaviour of 1,3-phenylene bis[4-(4-alkoxyphenyliminomethyl)benzoates] and related compounds

DSC and X-ray diffraction studies on a series of 1,3-phenylene bis[4-(4-alkoxyphenyliminomethyl)benzoates] are presented. The only mesophase exhibited by the methoxy to hexadecyloxy homologues is of the smectic C type. The reversal of the iminomethyl linkage reduces drastically the incidence of a mesophase; that is, only the first five homologous members exhibit a smectic C phase in the series of 1,3-phenylene bis[4-(4-alkoxybenzylideneamino)benzoates]. Almost all the members in the second series become nematogenic by the chloro substitution at the 4-position of the 1,3-phenylene moiety. In addition, a smectic C phase is observable for the ethoxy to pentyloxy and also the tetradecyloxy and hexadecyloxy members. The second chloro-substituent introduced to the 6-position of the same central ring eliminates completely the smectic C phase and enhances the nematic thermal stability.     

New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

Effect of the variation of swallow-tailed groups on the mesomorphic and electro-optical properties of chiral compounds derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid

Three homologous series of chiral swallow-tailed compounds, alkyl (S)-2-{6-[4-(4′-alkoxyphenyl)benzoyloxy]-2-naphthyl}propionates, (S)HNP(p,n,q) derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid in conjugation with a variety of swallow-tailed groups, attached to the external side of the chiral centre, have been synthesized and their mesomorphic and electro-optical properties studied. Both (S)HNP(p,1,2) and (S)HNP(p,1,3) exhibited an enantiotropic antiferroelectric SmC*_A phase. This implys that the swallow-tailed groups in the molecules favour zigzag pairing of the molecules in the smectic phase. The maximum P _S values of compounds (S)HNP(p,1,2) in the antiferroelectric phase were measured in the range 21–30 nC cm^-2; those of compounds (S)HNP(p,1,3) were in the range 15–23 nC cm^-2, indicating that these chiral compounds possess low polarity. The electro-optical response of the compounds in the antiferroelectric SmC*_A phase displayed thresholdless V-shaped switching.     

Liquid crystalline compounds with V-shaped molecular structures: synthesis and characterization of new azo compounds

The synthesis and mesomorphic properties of a series of 1,2-phenylene bis[4-(4-alkyloxyphenylazo)benzoates] are reported. The mesophases exhibited by these bent-shaped azo compounds are identified as nematic, smectic A and crystal E phases. All these compounds have fairly low transition temperatures, and so are suitable for physical studies. It has been concluded that the -CH N- linkage can be more conducive to mesomorphism compared with the -N N- linkage.     

The kinetics of the E-Z-E isomerisation and liquid-crystalline properties of selected azobenzene derivatives investigated by the prism of the ester group inversion

Two new groups of azobenzene ester derivatives were synthesised: alkyl 4-[4-(nonyloxy)phenyl]diazenyl]benzoates and 4-[4-(nonyloxy)phenyl]diazenyl]phenyl alkanoates. All 35 presented homologues are mesogenic. Moreover, some of the above-mentioned compounds exhibit rich liquid-crystalline polymorphism likewise tetramorphism. During this investigation by the use of polarising optical microscopy, differential scanning calorimetry and X-Ray studies, six types of mesophases were detected: nematic, smectics (A, C, I, F) and G. Furthermore, due to the presence of the photosensitive azo moiety, the E–Z isomerisation reaction is possible. This process, which is initiated by the UV irradiation, causes significant changes in the UV-Vis absorption spectra of investigated compounds. However, the photoisomerisation is a reversible process and in the dark the thermal relaxation of Z isomer takes place. Based on the achieved data, the kinetic constants of the isomerisation and relaxation processes were calculated. It shows that conversion of the ester bond makes some changes in the optical properties. The shift of about 7 nm of the absorbance maximum was observed. Surprisingly, the inversion of the ester group has significant influence on the liquid-crystalline polymorphism replacing one mesophase (for benzoates) into four (for alkanoates).     

Esters derived from 7-decanoyloxychromone-3-carboxylic acid: synthesis and mesomorphic properties

The synthesis and liquid crystalline properties of a new series of calamitic liquid crystals containing 4-H-benzopyran-4-one (chromone) within the central core is reported. The first homologue in the series display SmA phase (8a), the homologues (8b–e) exhibit SmA and SmC mesophases and the homologues (8f–h) exhibit only a SmC mesophase.     

Azomesogens containing an ethoxyethyl terminal chain: synthesis and characterization

Two homologous mesogenic series, the ethoxyethyl 4-(4'-n-alkoxyphenylazo)benzoates (I) and the ethoxyethyl [4-(4'-n-alkoxybenzoyloxy)phenylazo]-4'-benzoates (II), both containing a terminal ethoxyethyl chain, have been synthesized. In series I, all nine members synthesized exhibit only an enantiotropic smectic A mesophase. In series II, all 12 homologues exhibit an enantiotropic nematic mesophase; a smectic A phase appears in the n-butyloxy derivative as a enantiotropic phase and persists through to the n-hexadecyloxy member. The mesomorphic properties of both series are compared with each other and also with the properties of other structurally related series to evaluate the effects of the ethoxyethyl chain on mesomorphism.     

The properties of phenyl cyclohexyl ferroelectric liquid crystals

To continue the search for novel series of ferroelectric liquid crystals, an additional two series of compounds, C S(+)-4-[(2-methylbutyl)phenyl]4'-trans-n-alkylcyclohexyl) benzoates and D S(+)-4-[(4-methylhexanoyl)phenyl]4'(4'-trans-n-alkylcyclohexyl) benzoates, where alkyl = C₅-C₆ are reported in this paper. Their mesomorphic properties have been characterized by optical textural observations and DSC. Some of these compounds show a C-S*_C-S_A-N*-I phase transition sequence. The effects of the alkyl chains on transition temperatures and optically active terminal groups on phase behaviour are discussed.     

Synthesis and mesomorphic properties of 7-acyloxy-3-(4-acyloxyphenyl)-4H-1-benzopyran-4-one

A new homologous series of 7-acyloxy-3-(4-acyloxyphenyl)-4H-1-benzopyran-4-ones was synthesized and characterized by elemental analysis and spectroscopic techniques along with thermal behaviour study using differential scanning calorimetry. Texture observation was performed under the polarizing optical microscope from which the derivatives were found to exhibit different molecular organizations as exemplified by various mesophases. Whilst the compounds containing butanoyloxy and hexanoyloxy groups behave as nematogens, the other compounds with heptanoyloxy and longer side chains show a SmC phase. The octadecanoyloxy derivative was the only member showing a monotropic SmC phase. The difference in phase behaviour is discussed based on the molecular structure and the presence of a lateral dipole which can be associated with the intermolecular interaction within the mesophase.     

Chiral liquid crystalline m-nitrotolans and tolans: synthesis and mesomorphic properties

Two homologous series, 4'-(4-n-alkoxybenzoyloxy)-4-substituted 3-nitrotolans (Ia-d) and 4'-(4-n-alkoxybenzoyloxy)-4-substituted tolans (IIa-c), with substituents (S)-2-methyl-1-butyl and n-alkyl, were synthesized by Sonogashira's coupling. Their mesomorphic behaviour is reported. The thermal stability of the series II is higher than that of series I. Series I melting points and clearing points are lower than those of series II. None of the chiral tolans or m-nitrotolans have an enantiotropic smectic C phase. When the chiral chains are changed to n-alkyl groups in compounds Ia,b and IIa, an enantiotropic smectic C phase is seen. All compounds have a nematic or cholesteric phase, and two homologues of series II present a monotropic smectic C phase with mosaic texture. The mesophases were characterized using optical polarized light microscopy and differential scanning calorimetry.     

1,4-Diaryl and Schiff's base [1,2,3]-triazole derivative liquid crystalline compounds

Regioselective synthesis of [1,2,3]-triazoles based on the 'click-reaction', involving the Cu(I)-catalysed 1,3-dipolar cycloaddition of aryl azide to terminal arylacetylenes, was successfully employed in the preparation of two series of non-linear mesogens, based on 1,4-diaryl-[1,2,3]-triazole (Ia-e) and with Schiff's base units (IIa-c). Their mesophases were characterized by polarizing optical microscopy and differential scanning calorimetry. All final compounds exhibited preferentially the SmC phase. In addition, compounds of series I showed weak blue fluorescence in solution (λ_{max. em.} = 380-386 nm) with poor quantum yields and a Stokes shift of around 90 nm.     

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.     

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 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.