Unsymmetrical dimers possessing a cholesteryl ester moiety and a difluoro-substituted biphenyl core: synthesis and mesomorphic behaviour

Some new unsymmetrical dimers consisting of a cholesteryl ester moiety, covalently linked to either a 4'-(2,3-difluoro-4-n-octyloxy) biphenyloxy or a 4'-(2,3-difluoro-4-n-decyloxy) biphenyloxy through odd-even parity paraffinic central spacers, have been synthesized and investigated for their mesomorphic behaviour. Except for one, all the dimers exhibit enantiotropic smectic A, twist grain boundary (TGB) and chiral nematic mesophases. Five of the eight unsymmetrical dimers synthesized show a chiral smectic C (SmC*) phase. Interestingly in some of the compounds the SmC* exists over a wide temperature range including room temperature. Among the eight compounds, a dimer having a C₇ central paraffinic spacer and a C₈ alkoxy terminal chain shows an enantiotropic twist grain boundary with SmC* blocks (TGB_C*) phase. It appears that the variation in the length of the spacer has a remarkable influence on the phase transition temperatures as well as on the mesomorphic behaviour.     

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.     

Synthesis and mesomorphic properties of some platinum(II) and oxovanadium(IV) complexes

The synthesis and mesomorphic properties of a homologous series of N-(2-hydroxy-4-n-alkoxybenzylidene)-4'-n-decylphenylanilines and their platinum(II) and oxovanadium(IV) complexes are reported. All the ligands and their metal chelates exhibit enantiotropic mesophases, predominantly smectic A and smectic C phases. The transition temperatures and enthalpies have been determined for most of the compounds. The platinum(II) complexes have higher melting points and mesophase thermal stabilities. However, the oxovanadium(IV) complexes have a wider thermal range for the mesophase. Both platinum(II) and oxovanadium(IV) complexes containing only a chain on the biphenyl moiety exhibit a nematic phase.     

Novel chiral liquid crystals based on amides and azo compounds derived from 2-amino-1,3,4-thiadiazoles: synthesis and mesomorphic properties

Novel chiral amides (Ia-Ie, II) and azo compounds (III, IV) with a 1,3,4-thiadiazole unit in the rigid core were synthesized and their liquid crystalline properties investigated by polarizing optical microscopy and differential scanning calorimetry. The amides Ia-Ie contain a chiral alkoxy chain derived from (R)-2-octanol and an achiral chain varying from 6 to 10 carbon atoms at the end of the rigid core. In amide II one of the terminal group is a chiral alkoxy chain derived from (S)-isoleucine and the other terminal substituent is an achiral n-decyloxy chain. Azo compounds III and IV contain an achiral n-decyloxy chain and a chiral alkoxy chain derived from (R)-2-octanol and (S)-isoleucine, respectively, at the end of the rigid core. The first homologue in the series of amides (Ia) exhibits enantiotropic smectic X (SmX)-chiral nematic (N*) dimorphism and the homologues Ib-Ie display enantiotropic SmX-chiral smectic C (SmC*)-N* mesomorphism. Amide II displays an enantiotropic smectic A phase. The azo compounds III and IV do not show smectic order and only an enantiotropic N* phase was observed. Thus, the mesomorphic behaviour depends on the nature of the central linkage and on the nature of the chiral alkoxy chain.     

Synthesis and characterization of homologous series with chiral (S)-1-methylpropyl terminal substituent

Homologous series of liquid crystalline azoesters and azomethine esters consisting of a (S)-1-methylpropyl group attached in one of the terminal positions have been synthesized and thermally characterized. All twenty-four derivatives from both series, namely, the 4-(4-n-alkoxybenzoyloxy)-4'-1-(S)-methylpropylazobenzenes and 4-(4-n-alkoxybenzoyloxy)benzylidene-4'-1-(S)-methylpropylanilines exhibit mesomorphism. The lower members of the homologous series show a chiral nematic phase while the higher members show smectic C*, smectic A as well as chiral nematic mesophases. The homologues have been characterized using IR, NMR and UV-Visible, spectroscopies, X-ray diffraction and DSC. Their mesomorphic properties are compared with those of structurally related homologous series.     

Azomesogens with methoxyethyl tail: Synthesis and characterization

Two new mesogenic homologous series are synthesized from methoxyethyl 4-(4′-hydroxyphenylazo) benzoate. In series I the phenolic -OH group is alkylated, whereas in series II it is esterified with 4-n-alkoxybenzoyl group. In series I, all the nine members synthesized exhibit only enantiotropic smectic A mesophase. In series II, all the twelve homologues exhibit enantiotropic nematic mesophase. Smectic A mesophase appears from then-decyloxy derivative as a enantiotropic phase and persists till the last n-hexadecyloxy member. The mesomorphic properties of both the series are compared with each other and also with the properties of other structurally related series to evaluate the effect of the methoxyethyl tail on mesomorphism.     

Unsymmetrical dimers possessing a cholesteryl ester moiety and a difluoro-substituted biphenyl core: synthesis and mesomorphic behaviour

Some new unsymmetrical dimers consisting of a cholesteryl ester moiety, covalently linked to either a 4′-(1,3-difluoro-4-n-octyloxy) biphenyloxy or a 4′-(2,3-difluoro-4-n-decyloxy) biphenyloxy through odd-even parity paraffinic central spacers, have been synthesized and investigated for their mesomorphic behaviour. Except for one, all the dimers exhibit enantiotropic smectic A, twist grain boundary (TGB) and chiral nematic mesophases. Five of the eight unsymmetrical dimers synthesized show a chiral smectic C (SmC*) phase. Interestingly in some of the compounds the SmC* exists over a wide temperature range including room temperature. Among the eight compounds, a dimer having a C₇ central paraffinic spacer and a C₈ alkoxy terminal chain shows an enantiotropic twist grain boundary with SmC* blocks (TGB_C*) phase. It appears that the variation in the length of the spacer has a remarkable influence on the phase transition temperatures as well as on the mesomorphic behaviour.     

Synthesis and mesomorphic properties of some esters of trans-4-n-alkoxycinnamic and trans-4-n-alkoxy-alpha-methylcinnamic acids exhibiting ferroelectric and antiferroelectric phases

The synthesis and mesomorphic properties of several homologues of (S)-(+)-1-methylheptyl 4-[4(trans-4-n-alkoxycinnamoyloxy)benzoyloxy]benzoates (series I) and (S)-(+)-1-methylheptyl 4-[4-(trans-4-n-alkoxy-alpha-methylcinnamoyloxy)benzoyloxy]benzoates (series II) are described. The influence of the alpha -methyl group on the different mesophases and the clearing temperatures has been evaluated. Many homologues of both the series show a ferroelectric chiral smectic C (SmC*) phase while the antiferroelectric smectic C phase (SmC*A) is exhibited by compounds of series I. The mesophases have been identified by optical polarizing microscopy, differential scanning calorimetry and miscibility studies. The spontaneous polarization, the helical pitch and the tilt angle of two of the compounds have also been measured.     

Ferroelectric liquid crystalline phase transition of (S)-hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy) cyclotriphosphazene

(S)-Hexakis(4-(4'-(6-methyl)octyloxy)biphenoxy)cyclotriphosphazene (SMOCP) was synthesized in a search for new ferroelectric liquid crystalline compounds. We found an enantiotropic ferroelectric smectic C* phase between 419 and 441 K in SMOCP by using polarizing microscopy and DSC measurements. The spontaneous polarization was estimated to be -130.5 μCm^-2 at 437.6 K, several times larger than that of DOBAMBC ((S)-2-methylbutyl 4-(4'-decyloxybenzylidene)aminocinnamate.     

Liquid crystalline properties of 4-isopropyl- and 4-isopropoxy- N -(4- n -alkoxysalicylidene)anilines

New homologous series of 4-isopropyl- and 4-isopropoxy- N -(4- n -alkoxysalicylidene)anilines were synthesized. The phase transitions of these homologues were determined by differential scanning calorimetry and polarizing optical microscopy. No enantiotropic liquid crystalline phases were observed for homologues having a terminal isopropyl group; as the terminal alkoxyl chain is lengthened, smectic C and nematic phases occur monotropically. The members with an isopropoxy substituent exhibit an enantiotropic nematic phase as the terminal alkoxyl chain is lengthened; the octyloxy member exhibits a monotropic smectic C phase as well as an enantiotropic nematic state.     

Liquid crystalline thiadiazole derivatives: new ferroelectric thiadiazole derivatives

A series of optically active thiadiazole Schiff's bases were prepared and their liquid crystalline properties were studied. Chirality was achieved by introducing an asymmetric carbon atom into the alkoxy group. Thus, 2-( p -active-alkoxyphenyl-imine)-5-( p - n -alkoxy)phenyl-1,3,4-thiadiazoles were synthesized. Their structures were characterized using elemental analysis, and IR, 1 H NMR and mass spectroscopies; their thermal properties were determined using DSC and polarized light microscopy. All the compounds are enantiotropic liquid crystals, and most of them exhibited both chiral smectic C* and cholesteric mesophases. Only one of them did not show a smectic C* 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.     

4-(5-Alkyl-2-pyridinyl)phenyl alkanoates: Some novel smectic materials for display devices

Abstract

Three homologous series of 4-(5-alkyl-2-pyridinyl)phenyl alkanoates have been prepared. The synthesis and the liquid crystal transition temperatures of these esters are reported. Many members of these three ester series exhibit enantiotropic, wide range smectic F mesophases and some narrow range smectic C mesophases. However, in admixture with a chiral smectic C base mixture, the esters often induce a substantial increase in the chiral smectic C–smectic A transition temperature and, at the same time, decrease the temperature of crystallization. Thus, the temperature range of the chiral smectic C mesophase is substantially extended at both high and low temperatures. Ordered smectic mesophases are only observed at very low temperatures, if at all. These chiral smectic C mixtures are characterized by short switching times in surface-stabilized ferroelectric liquid crystal displays (SSFLCD). These novel esters are of especial interest for short-pitch chiral smectic C mixtures for short pitch bistable ferroelectric liquid crystal displays (SBFLCD) with short response times.     

Synthesis of two naphthyl-containing homologous series of mesogenic ligands and the related metallomesogens containing Cu(II)

Two new naphthyl-containing homologous series of mesogenic ligands, the 4-n-alkoxy-2-hydroxybenzylidene-2'-naphthylamines (series I) and 4(4'-n-alkoxybenzoyloxy)-2-hydroxybenzylidene-2'-naphthylamines (series II), as well as the related metallomesogens of higher homologues containing a Cu(II) atom, have been synthesized. All the ligands and complexes were characterized by a combination of elemental analysis and standard spectroscopic methods. In series I, n-heptyloxy and n-octyloxy derivatives are non-mesogenic whereas the remaining higher members synthesized exhibit a monotropic nematic mesophase. In series II, all the members synthesized exhibit an enantiotropic nematic mesophase. All the metallomesogens of series I synthesized exhibit a monotropic smectic A mesophase, except for the n-octyloxy derivative, which is non-mesogenic, whereas metallomesogens of series II exhibit enantiotropic nematic mesophases up to the n-tetradecyloxy derivatives; the n-tetradecyloxy and n-hexadecyloxy derivatives also exhibit smectic C mesophases. All the members of series II and their metallomesogens exhibit mesophases with wide temperature ranges and greater thermal stability as compared to series I and their metallomesogens, respectively. The mesomorphic properties of both the present series and their metallomesogens are compared with each other and with other structurally related series to evaluate the effect of the naphthalene moiety on mesomorphism.     

New Schiff's bases containing 1,3,4-thiadiazole and 1,3,4-oxadiazole units: a study of the effect of the heterocyclic ring and the position of the lateral alkoxy group on liquid crystalline properties

The synthesis of novel Schiff's bases incorporating the five-membered 1,3,4-thiadiazole (series 7, 9) and 1,3,4-oxadiazole (series 8, 10) rings have been prepared and their liquid crystalline properties studied. All compounds of series 7 exhibit an enantiotropic smectic C phase. No liquid crystalline properties were observed for the compounds of series 8-10. A study of the structure/mesomorphic activity relationship is also described.     

Synthesis and Mesomorphic Properties of Novel γ-Substituted β-Diketonates

The synthesis and mesomorphic properties of two series of novel γ-substituted β-diketonates have been reported. All of the compounds 2,4-dioxo-3-pentyl 4-[[4-(n-alkoxyl) cinnamoyl]oxy]cinnamatetes Ia-If (n=7-12) exhibit two monotropic phases(N and Sc) and have a wider mesophase range than the compounds 2,4-dioxo-3-pentyl 4-[[4-(n-alkoxyl) benzoyl]oxy] cinnamatetes Ⅱa-Ⅱf (n=7-12), which display one monotropic nematic phase (n=7-10) or an enantiotropic nematic phase for n=11 or two enantiotropic phases (N and Sc)for n=12.     

Synthesis and transition temperatures of novel fluorinated chiral liquid crystals containing 1,4-tetrafluorophenylene units

To continue the search for novel series of fluorinated ferroelectric liquid crystals, an additional two series of 4-[(S)-2-methylbutoxy]phenyl 4-[(4-n-alkoxy-2,3,5,6-tetrafluorophenyl)ethynyl] benzoates (C) and 4-(n-alkoxy)phenyl 4-[(4-(S)-2'-methylbutoxy-2,3,5,6-tetrafluorophenyl)] benzoates (D) have been synthesized. Polarizing microscopic textural observations and DSC measurements of the phase transitions of these novel compounds showed that compounds C were liquid crystals with a chiral nematic (N) phase and a monotropic chiral smectic C phase (S_c), and compounds D exhibited a chiral nematic (N) phase.     

Synthesis and liquid crystalline investigation of chiral 6-alkoxy-2-naphathoic acid derivatives

A two new series of materials with a chiral fragment derived from ((S)-(─)-2-methyl-1-butanol and 6-alkoxy-2-naphathoic acid as the molecular core was synthesised and investigated. All the homologues exhibited enantiotropic mesomorphism. Chiral smectic C (SmC*), smectic A (SmA) and chiral nematic (N*) phases were observed in different homologues. All the compounds were characterised by spectroscopic and elemental analysis. Thermal investigations and mesophase characterisations for all the compounds were carried out by the combination of DSC and POM analysis. The effects of the central linkage and various terminal normal alkyl chains with its structurally related compounds have been discussed.     

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.     

Asymmetric dimeric liquid crystals The preparation and properties of the α-(4-cyanobiphenyl-4'-oxy)-ω-(4-n-alkylanilinebenzylidene-4'-oxy)hexanes

Abstract

The first eleven members of the homologous series of α-(4-cyanobiphenyl-4'-oxy)-ω-(4-n-alkylanilinebenzylidene-4'-oxy)hexanes have been synthesized. The compounds are all enantiotropic nematogens and, with the exception of the heptyl, octyl and nonyl homologues, exhibit smectic phases. The thermal stability of the smectic A phase initially increases with the length of the terminal alkyl chain, passes through a maximum and then falls dramatically before disappearing. The smectic A phase subsequently reappears with the decyl homologue which has the highest smectic A-nematic transition temperature of the series. In order to understand this unusual behavior we have determined the entropies of transition for the compounds and we have measured the layer spacing of the smectic A phase for three of them.