Mesogenic Unsymmetric dimers containing cholesteryl ester and tolane moieties

Among unsymmetric oligomesogens, chiral dimers formed by connecting a cholesteryl ester fragment with various aromatic mesogenic cores through a polymethylene spacer have been attracting much attention due to their remarkable thermal behaviour. In particular, dimers containing a diphenylacetylene segment having an alkoxy chain have shown interesting mesomorphic behaviour. In view of this a new series of unsymmetric dimers consisting of a diphenylacetylene moiety having an alkyl chain and a cholesteryl ester unit joined through a paraffinic spacer have been synthesized and their liquid crystalline properties characterized. The lengths of the central methylene spacer (C₃, C₄, C₅ and C₇) as well as that of the alkyl chain (n-butyl, n-pentyl, n-hexyl and n-heptyl) have been varied to establish structure–property relationships. These investigations have revealed that all the dimers exhibit smectic A, twist grain boundary and chiral neamtic (N*) phases with the exception of one of the dimers for which only the N* phase was observed. Some differences in the mesomorphic properties of the unsymmetric dimers containing odd or even parity methylene spacers have been observed. The majority of dimers having an even (C₄) parity paraffinic spacer show a blue phase while the dimers with odd (C₃, C₅ and C₇) parity spacers exhibit the chiral smectic (SmC*) phase. In some cases, the SmC* phase exists well below (?60°C) and above room temperature.     

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.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

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.     

Liquid crystal dimers possessing chiral rod-like anisometric segments: synthesis, characterization and electro-optic behaviour

Several new optically active liquid crystal dimers comprising pro-mesogenic cholesterol and a chiral diphenylacetylene (tolane) segment, covalently linked in an end-to-end fashion through a flexible spacer, have been synthesized and investigated for their mesomorphic behaviour with the aid of optical, calorimetric and X-ray diffraction studies. Five unsymmetrical dimers, designed on the basis of recent work, involve molecular structural variations of the tolane mesogenic entity with a view to stabilizing a wide thermal range smectic A (SmA) phase featuring the electroclinic effect. Three different chiral chains, namely, (S)-1-methylheptyloxy, (S)-2-methylbutyloxy, (3S)-3,7-dimethyloctyloxy, with or without polar (nitro or fluoro) lateral substituents, were incorporated, while keeping the length (C₆) of the spacer constant. As expected, all the dimers exhibited a SmA phase. A few also showed chiral nematic (N*) and/or twist grain boundary and/or chiral smectic C (SmC*) phases. Remarkably, some of these oligomesogens, upon melting, had a stable SmA phase over a wide thermal interval (100-150°C); this state seems to be stable for a long period of time. Electro-optic studies, including optical tilt angle as well as temporal response as a function of temperature, were carried out in the SmA phase. The SmC* phase was also investigated for its electrical switching and optical tilt angle, as well as spontaneous polarization as a function of temperature. These studies showed that the mesophase response to an applied field is weak and is independent of variations in the dimer investigated.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd–even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

Cholesterol-containing liquid crystal dimers with ether linkages between the spacer and mesogenic units

Three series of chiral liquid crystalline dimers were investigated, having a cholesteryl and a cyanobiphenylyl, butoxybiphenylyl or hexyloxybiphenylyl group connected to a variable alkyl spacer through ether linkages. Their properties were compared with those of the corresponding ester derivatives. The phase behaviour of compounds with ether and ester linkages is comparable, showing N* and SmA phases. The melting points of the compounds with ether linkages are in the same range as those of the ester compounds, but the liquid crystal transition temperatures are lower. The smectic layer spacings and smectic ordering properties are also similar. The cyanobiphenylyl compounds have an interdigitated SmA layer structure, which shows a small odd-even effect with spacer parity. The alkoxybiphenylyl compounds have a monolayer SmA phase for short spacers and an intercalated SmA phase for longer spacers. The selective reflection wavelengths of the chiral nematic phase of the ether compounds are lower than those of the corresponding ester compounds. The transition from N* to interdigitated or monolayer SmA is accompanied by a strong increase in the selective reflection wavelength, indicative of an intermediate TGB phase. This is absent for the transition from N* to intercalated SmA.     

Salicylaldimine-based symmetric dimers: synthesis and thermal behaviour

Several symmetrical dimers comprised of salicylaldimine-moieties connected through ester linkages to the termini of odd-parity alkanediols have been synthesized and investigated for their thermal behaviour. In order to understand the structure-property relations, the lengths of the central alkylene spacers (C₃ and C₅) as well as those of the terminal alkoxy chains (C₆ to C₂₂) have been varied. The dimers with a C₃-alkylene spacer are non-liquid crystalline, while some of the compounds having a C₅-alkylene spacer exhibit liquid crystalline properties. The dimer, with a C₅-alkylene spacer and C₆-alkoxy tails, shows an intercalated smectic C (SmC_c) phase, whereas the C₈, C₁₀, C₁₁, and C₁₂ homologues are non-mesomorphic. The higher homologues of this series with C₁₆, C₁₈, C₂₀ and C₂₂ alkoxy tails show a mesophase that has the signatures of a two-dimensional banana (B₁) phase. This mesophase is enantiotropic in the C₁₆ and C₁₈ homologues while it is monotropic in the other homologues. In these dimers, the spacer length has a remarkable influence on the thermal behaviour.     

Influence of spacer and terminal group lengths on the smectic ordering of cholesterol-containing dimer liquid crystals

The smectic properties of four series of dimer liquid crystals containing cholesteryl and biphenylyl groups were investigated by polarization microscopy, DSC and X-ray diffraction. Compounds that contain the strongly dipolar cyanobiphenylyl group exhibit a smectic layer spacing that is about 1.7 times the length of the molecule. Three series of alkoxybiphenylylcontaining dimers exhibit two other smectic modifications. For short spacers, a smectic layer spacing is observed that is about the same length as the molecule and for long spacers the smectic layer spacing is about half the length of the molecule. In the latter cases the entropy change at the SmA-N* transition is clearly larger than for the compounds with the other smectic modifications. One or two compounds in each alkoxybiphenylyl-containing series, that have similar spacer length and terminal group length and have an odd number of flexible units in the spacer, exhibit only a chiral nematic phase, and no smectic phase.     

Synthesis and thermal behaviour of salicylaldimine-based liquid crystalline symmetrical dimers

A series of symmetrical dimers consisting of salicylaldimine moieties connected by flexible alkylene central spacer via ether linkages has been synthesized. In order to validate the empirical rule suggested by Date et al. to account for the smectic behaviour of such dimers, the chain length of the terminal alkoxy chain has been kept constant (C₈) while the number of methylene units in the central spacer was varied from C₃ to C₁₁. Another aim of the present investigation was to understand structure-property relationship in these dimers in which the salicylaldimine mesogenic segment has been used for the first time in dimers. The mesomorphic behaviour of these dimers was evaluated using optical microscopy and differential scanning calorimetry and the structure of some of the mesophases has been further investigated with the help of X-ray diffraction. Our studies reveal that the dimers consisting of 3 to 8 methylene units in the flexible spacer show only smectic (smectic C and smectic A) phases. For the dimers containing 4, 6 and 8 methylene units in the central spacer, a unique filament growth pattern has been observed in the smectic A phase while cooling from the isotropic phase. The dimers containing of C₉ to C₁₁ methylene groups exhibit the nematic phase in addition to smectic modifications. This observation indicates that when the terminal chains are shorter than the spacer, the tendency to form smectic phases is not fully extinguished but is perhaps reduced.     

Non-symmetric chiral isoflavone dimers: synthesis,characterisation and mesomorphic behaviour

A new series of non-symmetric chiral isoflavone-based liquid crystalline dimers, α-(2-methylbutyl-4′-(4″-phenyloxy)benzoate)-ω-(3-(4′-decyloxyphenyl)-4H-1-benzopyran-4-one-7-oxy)alkanes, with 3–12 carbon atoms in the alkyloxy spacer, have been synthesised. A pronounced odd–even effect for the phase transition temperatures upon varying the spacer length was observed. The short dimers exhibited monolayer smectic A (SmA) and smectic C (SmC*) phases while for longer homologues a chiral nematic (N*) phase was found. The temperature range of the nematic phase was broadened with elongation of the alkyl spacer. Stabilisation of the nematic phase resulted from competition between the monolayer and intercalated smectic structures. The SmA–SmC* phase transition was second order for all studied compounds with a cross over to the de Vries type behaviour for the shortest homologue.     

Liquid crystal dimers containing Cholesteryl and Triazole-containing mesogenic units

ABSTRACT

New liquid crystals categorised as cholesteryl dimers have been successfully synthesised through the reaction between cholesteryl 4-(prop-2-ynyloxy)benzoate moieties with n-azido(cholesteryloxy-carbonyl)alkane. All the dimers display enantiotropic mesophases. Whilst the odd-numbered dimers exhibit chiral nematic (N*), twisted grain boundary (TGB) and chiral smectic C (SmC*) phases, the even-numbered members from the same series show chiral smectic A and C. A detailed inspection on mesophase reveals that the chiral centres and the bent conformation of the odd-numbered members are essential for the induction of TGB phase. However, upon decreasing the temperature, the ratio of the transition temperatures (T_SmC*-SmA*/T_SmA*-I) is found to be 0.95, which indicate the second order transition according to the McMillan’s molecular theory. In addition, the X-ray diffraction study supports the presence of the smectic A phase on the even members rather than the N* by the appearance of the Bragg diffraction peaks at 190°C. A comparison study with the other analogues in which the cholesterol entity is substituted by azobenzene or biphenyl tails has been carried out to assess the relationship between the molecular structure and mesomorphic behaviour.     

Methylene- and ether-linked liquid crystal dimers II. Effects of mesogenic linking unit and terminal chain length

Four series of liquid crystal dimers have been prepared containing either ether-linked or methylene-linked spacers. Changing the spacer from being ether-linked, i.e. O(CH₂) _n O, to methylene-linked, i.e. (CH₂) _{n +2}, results in decreased nematic-isotropic transition temperatures, and this reduction is more pronounced for odd-membered spacers. By contrast, the entropy change associated with the nematic-isotropic transition is higher for an even-membered methylene-linked dimer than for the corresponding ether-linked material. This trend is reversed for odd members. These observations are completely in accord with the predictions of a theoretical model developed by Luckhurst and co-workers in which the only difference between the dimers is their shape. For the highly non-linear pentamethylene-linked dimers, only those with a short terminal chain exhibited fluid smectic behaviour, specifically, a monotropic alternating SmC structure which allowed for the efficient packing of the bent molecules. Once the terminal chain reached a value of m = 9, a modulated ordered smectic phase was observed. For even-membered dimers, which exhibit only nematic phases upon melting for short terminal chain lengths, smectic phase behaviour was promoted with increasing terminal chain length, as is conventionally observed. Even-membered ether-linked dimers exhibited a SmC phase whereas even-membered methylene-linked dimers exhibited an ordered smectic G/J phase. Thus, it would appear that the differences in the transitional properties of ether- and methylene-linked dimers can be accounted for largely in terms of geometrical factors.     

Synthesis and characterization of new ferroelectric liquid crystals containing a phenyl biphenyl carboxylate mesogenic group and oligooxyethylene spacers

Two series of ferroelectric liquid crystals containing a phenyl biphenyl carboxylate mesogenic group and oligooxyethylene spacers were synthesized. The mesomorphic behaviours of the compounds were characterized using differential scanning calorimetry (DSC), optical polarizing microscopy (POM) and powder X-ray diffraction measurements. These series all contain a smectic A (S_A), a chiral smectic C (S_C) and a crystal E (C_r E) phase sequence. The ordered smectic Cr E phase was observed for the short spacer chain (n = 0, 1, 2) homologues of the two series. Moreover, the mesomorphic properties are discussed as a function of the oligooxyethylene spacer length, and the position of the aromatic core rings. These results indicate that the structures with a rigid part (biphenyl group) closer to the flexible spacer chain (oxyethylene unit) tend to form the symmetrical smectic S_A and Cr E phases.     

Cholesterol-based dimeric liquid crystals: synthesis and mesomorphic behaviour

Chiral non-symmetric dimeric liquid crystals consisting of a cholesteryl ester moiety as chiral entity and a biphenyl aromatic core, interconnected through n-butyl (C₄) or n-pentyl (C₅) parity alkylene spacers, have been synthesized and investigated for their liquid crystalline properties. All the dimers exhibit enantiotropic mesophases. The first member of the dimers having the C₄ central spacer exhibit only the chiral nematic (N*) mesophase, while the higher homologues also show smectic A (SmA) and twist grain boundary (TGB) mesophases. The dimers of the other series containing the C₅ central spacer also have stable SmA, TGB and N* mesophases, except for the first which does not show the TGB phase. Both series of compounds show a weak odd-even effect with terminal alkyl chain substitution, while the spacer length has a marked influence on the phase transition temperatures.     

Synthesis and characterization of new ferroelectric liquid crystals containing a (2S)-2-[6-(4-hydroxybiphenyl-4'-carbonyloxy)-2'- naphthyl] propionate mesogenic group and oligo(oxyethylene) spacers

Three series of ferroelectric liquid crystals containing a (2S)-2-(6-(4-hydroxybiphenyl-4'-carbonyloxy)-2'-naphthyl)propionate mesogenic group and oligo(oxyethylene) spacers were synthesized. These obtained liquid crystal compounds were characterized by NMR, differential scanning calorimetry (DSC), optical polarized microscopy (POM), and X-ray powder diffraction measurements. Some of these materials containing four phenyl rings of ester cores (i.e. -Ph-Ph-COO-naph-) and chiral heptyl tail exhibited a rich mesomorphic behaviour, a blue phase (BP), a cholesteric phase (Ch), a smectic A (S_A), a twist grain boundary A (TGB_A), and a chiral smectic C (S_C*) phase. Another series containing four phenyl rings of ester cores and chiral butyl and pentyl chain tails revealed only a S_A phase and a S_C* phase. Moreover, a crystal E phase was observed in the short spacer chain (n = 0 or 1) homologues of three series of compounds. Also, the mesomorphism properties were discussed as a function of spacer units, numbers of aromatic rings of core, and different terminal asymmetric moieties.     

Influence of spacer and terminal group lengths on the smectic ordering of cholesterol-containing dimer liquid crystals

The smectic properties of four series of dimer liquid crystals containing cholesteryl and biphenylyl groups were investigated by polarization microscopy, DSC and X-ray diffraction. Compounds that contain the strongly dipolar cyanobiphenylyl group exhibit a smectic layer spacing that is about 1.7 times the length of the molecule. Three series of alkoxybiphenylylcontaining dimers exhibit two other smectic modifications. For short spacers, a smectic layer spacing is observed that is about the same length as the molecule and for long spacers the smectic layer spacing is about half the length of the molecule. In the latter cases the entropy change at the SmA-N* transition is clearly larger than for the compounds with the other smectic modifications. One or two compounds in each alkoxybiphenylyl-containing series, that have similar spacer length and terminal group length and have an odd number of flexible units in the spacer, exhibit only a chiral nematic phase, and no smectic 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.     

Organometallic chiral liquid crystals: bis4-[ω-(cholest-5-en-3-yloxycarbonyl)alkoxy]phenylethynylmercury complexes

We report the synthesis and thermal behaviour of the first chiral organometallic trimesogens having bis[(4-phenyl)ethynyl]mercury as the central core connected on either side to cholesteryl ester moieties through either even-even (C₄) or odd-odd (C₃, C₅ and C₇) central alkylene spacers. All the organomercury trimesogens exhibit a chiral nematic phase. These mercury complexes are extremely sensitive to heat, in a manner reminiscent of other reports.     

Liquid crystalline properties and dependence of transition temperatures on the length of the flexible alkylene spacer of symmetric dimers composed of bent-core units

Three new series of symmetric dimers composed of bent-core molecules connected by a flexible alkylene spacer have been synthesized and their mesomorphic properties studied. The effect of varying the length of the terminal chains for fixed odd and even spacers, as well as varying the spacer length for a fixed terminal chain length, on the mesomorphic properties has been investigated. Remarkably, all the dimers investigated show the same type of mesophase, which has been characterized as a Col_obP_F phase, on the basis of X-ray diffraction and electro-optical measurements. It is found that for a fixed spacer length, the thermal range of the mesophase increases with increase in the number of methylene units in the terminal chain. On the other hand, interestingly an odd-even effect is observed when the length of the flexible spacer is varied; dimers having an odd number of methylene units possess higher clearing points.