The intercalated smectic A phase. The liquid crystal properties of the α-(4-cyanobiphenyl-4'-yloxy)-ω)-(4-alkyloxycinnamoate)alkanes

A novel system of non-symmetric dimers containing 4-n-alkyloxy-substituted cinnamic acid and cyanobiphenyl groups has been studied. Two series were prepared: in one the flexible spacer was varied in length while the spacer was fixed. The spacer length has a profound influence on the nematic-isotropic transition temperature of these materials and a large odd-even effect is observed for the series. The terminal chain also plays a significant role in determining the liquid crystal phase behaviour: a smectic A phase is exhibited for the ethyl and propyl homologues, in addition to a nematic phase; this smectic phase vanishes for intermediate chain lengths but then reappears for the nonyl and decyl members of the series. X-ray diffraction has revealed the structure of the smectic A phase for the ethyl homologue to be intercalated, whereas that for the decyl compound is interdigitated. The existence of the intercalated smectic A phase has previously been explained in terms of a charge-transfer interaction between unlike mesogenic groups. However, for the non-symmetric liquid crystal dimers described here this specific interaction appears unlikely and we discuss, therefore, other possible mechanisms for the formation of intercalated smectic phases.     

The liquid crystal properties of symmetric and non-symmetric dimers based on the azobenzene mesogenic group

A novel system of symmetric and non-symmetric dimers containing azobenzene groups has been synthesized and studied in an attempt to understand further the molecular origins of the intercalated smectic phases. For the non-symmetric dimers, the lack of symmetry was derived solely from the differences in length of the two terminal alkyl chains. Both the spacer and terminal chain lengths were varied. The spacer length was found to exert a profound influence on the clearing temperatures of these materials and a large odd-even effect was observed for the series. The smectic A phase stability was observed to increase with the terminal chain length, yet decrease with increasing spacer length. X-ray diffraction has revealed the structure of the smectic A phase of both the symmetric and non-symmetric azobenzene dimers to be of the monolayer type and not intercalated. The existence of the intercalated phase has previously been explained in terms of either a charge-transfer interaction, or by an electrostatic quadrupolar interaction. However, it has been thought that it may also be the result of an excluded volume or space filling constraint. For the non-symmetric liquid crystal dimers described here, a charge-transfer interaction should be minimal, as should the stabilization from the quadrupolar interaction between the two mesogens. However, it appears that some sort of specific interaction is required to stabilize the intercalated structure.     

The liquid crystal properties of symmetric and non-symmetric dimers based on the azobenzene mesogenic group

A novel system of symmetric and non-symmetric dimers containing azobenzene groups has been synthesized and studied in an attempt to understand further the molecular origins of the intercalated smectic phases. For the non-symmetric dimers, the lack of symmetry was derived solely from the differences in length of the two terminal alkyl chains. Both the spacer and terminal chain lengths were varied. The spacer length was found to exert a profound influence on the clearing temperatures of these materials and a large odd-even effect was observed for the series. The smectic A phase stability was observed to increase with the terminal chain length, yet decrease with increasing spacer length. X-ray diffraction has revealed the structure of the smectic A phase of both the symmetric and non-symmetric azobenzene dimers to be of the monolayer type and not intercalated. The existence of the intercalated phase has previously been explained in terms of either a charge-transfer interaction, or by an electrostatic quadrupolar interaction. However, it has been thought that it may also be the result of an excluded volume or space filling constraint. For the non-symmetric liquid crystal dimers described here, a charge-transfer interaction should be minimal, as should the stabilization from the quadrupolar interaction between the two mesogens. However, it appears that some sort of specific interaction is required to stabilize the intercalated structure.     

The intercalated smectic A phase. The liquid crystal properties of the α-(4-cyanobiphenyl-4′-yloxy)-ω)-(4-alkyloxycinnamoate)alkanes

Abstract

A novel system of non-symmetric dimers containing 4-n-alkyloxy-substituted cinnamic acid and cyanobiphenyl groups has been studied. Two series were prepared: in one the flexible spacer was varied in length while the spacer was fixed. The spacer length has a profound influence on the nematic-isotropic transition temperature of these materials and a large odd-even effect is observed for the series. The terminal chain also plays a significant role in determining the liquid crystal phase behaviour: a smectic A phase is exhibited for the ethyl and propyl homologues, in addition to a nematic phase; this smectic phase vanishes for intermediate chain lengths but then reappears for the nonyl and decyl members of the series. X-ray diffraction has revealed the structure of the smectic A phase for the ethyl homologue to be intercalated, whereas that for the decyl compound is interdigitated. The existence of the intercalated smectic A phase has previously been explained in terms of a charge-transfer interaction between unlike mesogenic groups. However, for the non-symmetric liquid crystal dimers described here this specific interaction appears unlikely and we discuss, therefore, other possible mechanisms for the formation of intercalated smectic phases.     

Non-symmetric calamitic liquid crystal dimers containing troponoid and benzenoid units

Five types of non-symmetric calamitic dimers were synthesized to investigate the effect of the core structure and length of the spacer on mesomorphic properties. Two non-symmetric dimers containing a troponoid and benzenoid unit showed smectic A and C phases whereas the corresponding benzenoid dimers showed no mesophase. Non-symmetric dimers with a three-ring system showed smectic A and C phases with higher transition temperatures than the two-ring system. We propose packing models for these non-symmetric dimers by considering the direction of the dipole moments of the ring structures and microsegregation between the polar units and the non-polar chains.     

Dimeric liquid crystals with 5-(4-alkoxybenzoyloxy)tropone or 4-(4-alkoxybenzoyloxy)phenyl cores: evaluation of the tilt angles of the cores, spacers, and side chains

Two types of symmetric dimers with 5-(4-alkoxybenzoyloxy)tropone cores or with 4-(4-alkoxybenzoyloxy)phenyl cores were synthesized to evaluate the effect of the core structure and the length of the spacer on the mesomorphic properties. The former had smectic C phases whereas the latter had smectic C and F phases. Both types of dimer showed a remarkable odd-even effect on varying the spacer on the mesomorphic properties. Comparison of the thermal stability between them demonstrated that benzenoid twins are more stable than troponoid ones. The layer spacings of the smectic C phases were measured to determine the tilt angles of the core part, the spacer, and the side chains on changing the length of the spacer and the side chains. Troponoid dimers had a larger tilt angle of the core part of the smectic C phase than benzenoid twins, which lowered the thermal stability of the troponoid. Entropy changes of the smectic C phase to the isotropic liquid showed a contrast between troponoids and benzenoids. The former had smaller values and odd-even effects than the latter, which indicated that the former troponoids had a limited number of conformers in mesophases.     

Anomalies of periodicity in TGB structures in new liquid crystal dimers

Non-symmetric liquid crystal dimers consist of two different mesogenic units linked through a polymethylene flexible spacer. Our previous studies have shown that dimers containing a cholesteryl moiety as one of the mesogenic groups and a Schiff 's base unit as the second, exhibit a rich polymorphism and that several types of smectic packing are obtained depending on the molecular parameters: specifically, a smectic periodicity similar to the molecular length and an intercalated structure with a smectic parameter lower than half the molecular length can be obtained. The competition between these two incommensurate lengths can induce two-dimensional phases and/or an incommensurate smectic phase in which the two smectic periodicities coexist over a long range. Small modifications of the molecular structure can significantly influence the phase sequence. Here we have replaced the Schiff 's base by a tolan unit and the terminal alkyl chains by alkoxy chains. As a result, anomalies of periodicity are also observed in this new dimeric series, but they occur mainly in TGB structures.     

Thermal properties of non-symmetric bibenzoate liquid crystalline dimers

The liquid crystal behaviour of a family of non-symmetric liquid crystalline dimers is reported. These systems contain two bibenzoate rigid units that are linked to distinct terminal groups at one end, and to a flexible interconnecting spacer at the other. Several systems having different terminal and central chains are studied using calorimetric, microscopic and diffraction techniques. All the samples form phases with variable degrees of order (from low ordered smectic to crystalline phases) depending on the chemical constitution of the different segments. The influence of the length, parity and lateral substitution of the spacers on the transitional properties and the symmetry of the mesophases that are formed is analysed. It is found that a decrease in the transition temperatures and enthalpies occurs when the length of the flexible spacers increases, when lateral methyl substituents are introduced, or when the parity of the central spacer changes from an even to odd number of carbon atoms or ether groups. The arrangement of the mesogens and dissimilar flexible groups within the ordered structure is discussed with respect to the observed L/d ratios. Different values were obtained depending on the parity of the central spacer and on the degree of order. Interpenetrated structures, in which the flexible groups of different lengths are mixed, seem to be compatible with low ordered smectic phases, but sterically disfavoured when constructing crystalline phases.     

Synthesis and characterization of non‐symmetric chiral dimers

A new class of cholesterol‐based non‐symmetric dimers have been synthesized and characterized. They comprise O‐alkylated cinnamic acid and pro‐mesogenic cholesterol segments interlinked covalently through a methylene spacer varying in its length and parity. All the dimers and some of the key precursors have been studied for their phase behaviour. All the intermediates show mesomorphism. Importantly, the thermal properties of dimers are found to be critically dependent on the parity of the flexible spacer. The dimers with odd‐parity spacer display chiral nematic and/or twist grain boundary phases. In contrast, the dimers with even‐parity spacer are either crystalline or exhibit metastable chiral nematic and/or twist grain boundary phases with the exception of one compound for which two unknown mesophases have been observed. The odd–even effect was found to be indistinct for selective reflection wavelengths of the chiral nematic phase. For some dimers, a variation in the pitch of the chiral nematic phase as a function of temperature was observed. Cyclic voltammetry experiments revealed the electrochemical properties of a representative liquid crystal dimer.     

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.     

Liquid crystalline dimers with bent-core mesogenic units

Two series of dimers, in which two identical aromatic bent core mesogenic units are connected via an organosiloxane or an alkylene spacer, have been investigated. The dimers with a spacer consisting of a trisiloxane central group and relatively long alkylene groups show an intercalated tilted smectic structure. The layer spacings appear to be very weakly dependent on the terminal chain lengths. In these dimers the smectic phase is stabilized for the compounds with a short terminal chain. Dimers with an aliphatic alkylene spacer are liquid crystalline only when the spacer is relatively short and the terminal chains are long. For these dimers a monolayer tilted smectic phase is observed.     

Dimesogenic compounds with an electron-attracting terminal group

Non-symmetric dimesogens composed of a classical aromatic mesogenic unit linked to a cholesteryl moiety by a flexible spacer form several types of smectic periodicities: one is connected to the cholesteryl length and the other to the length of the associated dimesogens. In some peculiar cases, anomalies of periodicity resulting from the competition between these incommensurate lengths are observed through the occurrence of two-dimensional modulated phases or incommensurate low ordered smectic phases (S_ic). As part of our continuing effort to understand the influence on the smectic arrangement of the molecular parameters of such non-symmetric dimesogens, new homologues with a cholesteryl unit linked by a pentamethylene spacer to an aromatic mesogenic moiety bearing different electron attracting terminal groups have been prepared. For these compounds, only the periodicity resulting from the associated dimesogens is observed. Nevertheless, an incommensurate smectic phase can be induced by mixing one of these compounds with another appropriate dimesogen. Molecular mechanics calculations suggest that the origin of the different smectic structures is strongly connected to the repartition of electrostatic potential along the dimesogen.     

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.     

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.     

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.     

Odd liquid crystalline dimers can be linear

The crystal and molecular structures of two liquid crystalline symmetric dimers containing the mesogenic group α,α′‐dimethylbenzalazine and flexible polymethylenic spacers of different parity (even and odd) are reported. They show nematic phases with strong odd–even effects. The unusual result we have found is that the odd dimer crystallizes adopting a molecular conformation in which the two mesogenic groups are aligned with respect to each other, as for the even dimer. The crystal packing of the two dimers is also analogous.     

Effect of introducing thioether linkages on the molecular organization of chiral twin liquid crystals

Novel symmetric and non-symmetric chiral twin compounds possessing one or two thioether groups in a central spacer were prepared, and the effect of substituting oxygen for sulphur on the liquid crystalline properties investigated. Chiral twin compounds possessing an alkylsulphanyl spacer showed an antiferroelectric phase exclusively. However, replacing the alkyloxy chain of the analogous monomer by the alkylsulphanyl chain has no significant effect on the phase transition behaviour, i.e. both of the monomers showed the ferro- and ferri-electric phases as well as the antiferroelectric phase. Thus, different effects of introducing the thioether linkage were for the first time observed between twin and monomeric systems. The introduction of oxygen or sulphur atoms into the central alkyl spacer of the chiral twin was also investigated, and these modifications were found to stabilize the SmA phase. Furthermore, the twin compound possessing a thiaalkyl spacer showed two different molecular assemblies in the smectic A phase.     

Why do non-symmetric dimers intercalate? The synthesis and characterisation of the α-(4-benzylidene-substituted-aniline-4′-oxy)-ω-(2-methylbutyl-4′-(4″-phenyl)benzoateoxy)alkanes

Ten new non-symmetric liquid crystal dimers belonging to the family of compounds α-(4-benzylidene-substituted-aniline-4′-oxy)-ω-(2-methylbutyl-4′-(4″-phenyl)benzoateoxy)-alkanes have been synthesised and their transitional properties characterised. The dimers contain either a hexamethylene or octamethylene spacer, while the terminal substituents on the 4-benzylideneaniline fragment are H, CH₃, F, Cl and Br. The unsubstituted dimers are not liquid crystalline, while the remaining compounds exhibit enantiotropic nematic behaviour. The trends in the clearing temperatures, according to the chemical nature of the terminal substituent, are largely consistent with those established for conventional low molar mass liquid crystals. Three of the dimers also exhibit an intercalated smectic A phase, specifically the two bromo-substituted dimers and the chloro-substituted dimer containing a hexamethylene spacer. The driving force for the formation of this phase is considered to be, at least in part, the specific anisotropic interaction between the unlike mesogenic units. The absence of smectic behaviour for the isosteric methyl-substituted dimers reveals that steric factors alone cannot stabilise the intercalated smectic A phase.     

Liquid crystals: a chemical physicist's view

This paper has allowed me the rare opportunity and pleasure of acknowledging those who have played important roles in my scientific career. It has also enabled me to report work in the field of liquid crystals which has gone unpublished. The particular topics have been selected because they illustrate the areas of liquid crystal science with which I have been especially concerned. The predicted phase diagram of mixtures of rods and spheres is both intricate and interesting. The ability to test these predictions experimentally has required the use of quasi-spherical solutes such as tetraethyltin. The reasons for the failure of the experiments to conform to theory are investigated and explained in terms of the orientational order of this flexible molecule, determined using deuterium NMR spectroscopy. The tetrapodes are more exotic tetrahedral structures in which four mesogenic groups are linked to a central atom or group. The massive flexibility of such molecules poses a severe problem for the prediction of their liquid crystal behaviour. Here a solution to this problem is presented and used to predict the dependence of the transitional properties of the tetrapodes on the spacer length and the mode of its attachment to the mesogenic group. The same molecular field approach has been employed to predict the variation of the transitional properties of liquid crystal dimers with the length of the spacer. It is found that for spacers containing about 12 or more atoms the odd-even effect predicted for the transitional properties varies significantly depending on the model used to describe the spacer conformation. That is, whether the torsional angles defining the conformations are taken to be discrete or continuous. Cyanobiphenyl dimers with spacers containing up to 24 atoms have been synthesized to test these predictions. The Gay-Berne potential has proved to be an important model with which to study liquid crystal behaviour using simulation techniques. By joining two Gay-Berne particles together with a flexible ethane link we have constructed a Gay-Berne dimer and have been able to explore the properties of this mesogen. In particular its phase behaviour, the novel structure of the smectic A phase and how the conformational distribution alters with the phase have been studied. Despite its attractive features there are relatively simple systems for which the Gay-Berne potential is not suitable. These include molecules with a spherocylindrical shape and those with a sphere embedded at the centre of such a structure. In fact the shapes of many mesogenic molecules approximate to the former, and certain metallomesogenic molecules have shapes like the latter. The novel Corner S-function potential provides a valuable way to represent such cylindrically symmetric shapes and we use this to simulate the behaviour of these systems. It is found that the sphere has a major influence on the phase behaviour as well as on the crystal structure.