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.     

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.     

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.     

Effect of terminal aryl rings of liquid crystal trimers on liquid crystalline properties

Liquid crystalline properties of five series of biphenyl derivatives connected with p-nitrophenyl, phenyl, 2-naphthyl, 9-phenathryl and bromo as the terminal groups via flexible spacers were studied. All the compounds exhibited nematic phase. The nematic–isotropic or isotropic–nematic transition properties resulted in an odd–even effect as the length of the spacers was varied, in which the even members exhibited higher values, for the compounds with p-nitrophenyl, phenyl, 2-naphthyl and 9-phenanthryl groups, while the transitional properties of the compounds substituted with bromo atom as the terminal group instead of the aryl groups did not show such odd–even effect. These results suggest that the aryl rings, such as p-nitrophenyl, phenyl, 2-naphthyl and 9-phenanthryl groups, play a role of mesogen while the terminal bromo atom does not. The effect of the terminal aryl rings on the liquid crystalline properties will be reported.     

Gelation is crucially dependent on functional group orientation and may be tuned by anion binding

The gelation ability of a series of chiral bis(urea) gels alternates between even and odd chain length and for the even numbered spacers the rheological characteristics can be tuned by the addition of anions according to the anion binding constant.     

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.     

Effects of combining of different flexible spacers in liquid crystal trimers and tetramers on transition properties

Liquid crystal trimers and tetramers containing two kinds of flexible spacers, namely O(CH₂) _m O and COO(CH₂) _n O, were divided into four classes according to the odd/even nature of the number of atoms in the flexible spacers: specifically, even–even, odd–odd, even–odd, and odd–even trimers, and even–even–even, odd–odd–odd, odd–even–odd, and even–odd–even tetramers. The transition properties of the four types of trimers and of tetramers were compared. Although the nematic–isotropic transition temperature and the associated entropy changes were primarily related to the number of the even-membered flexible spacers in these molecules, the different combinations of the flexible spacers significantly affected their transition properties.     

Odd-even effects in the phase transition behaviour of novel U-shaped liquid crystals

A homologous series of U-shaped dimeric liquid crystals in which two mesogenic groups are connected via catechol has been prepared and the effects of terminal alkyl chains, alkyl spacers and core structures on the transition properties investigated by means of optical microscopy and differential scanning calorimetry. The phase sequence exhibits a pronounced odd-even effect as the length and parity of the spacers is varied, in which the even members favour the nematic and smectic C phases, whereas the odd members favour the nematic and smectic A phases. We discuss the transition behaviour of the U-shaped compounds in terms of molecular shape.     

CRYSTALLINE MORPHOLOGY IN A SERIES OF CH3-SUBSTITUTED THERMOTROPIC AROMATIC POLYESTERS WITH EVEN AND ODD FLEXIBLE SPACERS*

 Crystalline morphology in a series of CH₃-substituted main chain thermotropic aromatic polyesters with even and odd numbered methylene spacers has been studied by polarizing optical microscopy (POM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). On crystallization from solution evaporation spherulites of radial structure were observed in the polymers with even numbered spacers, but spherulites with concentric rings form in the polymer with odd numbered spacers. Both spherulites have a lamellar structure, which is about 10 nm in thickness. On crystallization from nematic glassy state spherulites can not be grown; lamellar structure was only observed around disclinations in a specimen during crystallization. In the case of crystallization from nematic melt two types of spherulites can be observed for the sample with even numbered spacers. For the sample with odd numbered spacers spherulites can not be formed, but only irregular crystallites.     

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.     

Crystal and molecular structures of four model compounds for liquid crystal dimers with a methylene spacer of various lengths

The crystal and molecular structures of four model compounds for liquid crystal dimers namely, 4,4-[octyl]bis-acetophenone (B(AcP)8), 4,4-[heptyl]bis-acetophenone (B(AcP)7), 4,4-[hexyl]bis-acetophenone (B(AcP)6), and 1,1-(1,6-hexyldion)bis-benzene (DP6D), have been determined in order to gain an insight into observed differences in the textures of liquid crystalline phases of compounds with odd and even methylene spacers. All four compounds exhibit extended conformations with an all-trans conformation of the methylene chain but a twist between phenyl rings of about 125°, except DP6D for which the benzene groups lie in plane with the methylene chain. Half a molecule is necessary to represent the asymmetric unit of compounds with even numbers n of methylene groups in the spacer and belong to centrosymmetric space groups. The model compound with an odd value of n is non-centrosymmetric and shows another type of packing arrangement which may cause different textures and behaviour for dimesogenic compounds in the liquid crystalline state.     

Influence of spacer lengths on the properties of chiral triplet liquid crystals based on estradiol

A series of 3-[ω-(4-cyanobiphenyl-4'-yloxy)alkyl] ethers of estradiol 17-[ω(4-cyanobiphenyl-4'-yloxy)alkanoates] with variable spacers has been prepared as chiral triplet liquid crystals. The compounds show very broad range cholesteric phases and are transformed into cholesteric glasses at room temperature. They exhibit odd-even effects for their cholesteric-isotropic transition temperatures and the associated entropy changes as a function of spacer length. The odd-even effects are observed upon changing the parity of both the ester and of the ether spacer. The best ordering is observed for compounds with an even number of methylene groups both in the ester and the ether spacer. In these cases the three mesogen units are oriented more or less parallel when the alkyl spacers are in the all-trans-conformations. Odd-even effects are also observed for the selective reflection wavelength of the planar cholesteric phase, depending on the parity of both spacers. For several compounds with short spacers the selective reflection wavelength increases strongly with temperature, whereas for other compounds this is almost temperature independent.     

Spacer length dependence of TGBC* and SmA phases in cholesteryl and dihydrocholesteryl-containing trimer liquid crystals

Two series of trimer liquid crystals were investigated that contain a biphenylyl central group and two cholesteryl or dihydrocholesteryl terminal mesogenic groups. Only compounds with even spacers were investigated. The dihydrocholesteryl-containing trimers show a triply intercalated smectic A (SmA) phase when the spacer lengths are greater than 8, whereas the cholesteryl-containing trimers exhibit this triply intercalated SmA phase when the spacer lengths are more than 6. With shorter spacers, a twist grain boundary C* (TGBC*) phase was found. This is revealed by the formation of a typical dotted square grid pattern upon cooling from the chiral nematic (N*) phase in the planar texture. The dots are spaced by a distance of about 1.5-1.8 µm. Upon cooling from the N* phase in the focal conic texture a striped pattern is observed with the same spacing. X-ray diffraction revealed a repeat distance for the TGBC* phase that corresponds with a monolayer ordering. The results show that the weaker interaction between the dihydrocholesteryl groups compared with cholesteryl groups or longer spacers destabilize the monolayer TGBC* phase.     

Phase transitional behaviour of S-shaped oligomers incorporating biphenylene and cholesterol entities

A new series of symmetrical S-shaped oligomers 4,4′-bis[(5-cholesteryloxycarbonylpentyl alkoxy)hexyloxy]biphenyl consisting of outer spacers –(COCH₂)_n– as well as an inner spacer –(CH₂)₆– has been synthesised. Their liquid crystalline properties and phase transition temperatures with associated enthalpy changes are recorded. The outer spacers are varied from n = 5–8 to 10 and 11. The compounds with even spacer exhibit enantiotropic phase and oligomers with odd parity display monotropic phase. The oligomers with odd membered n = 5, 7 and 11 exhibit N* and SmC* phases upon cooling. Whilst upon heating, the homologues with even-numbered member n = 6 and 10 show N* phase and upon cooling, both compounds exhibit N* and SmC* phases. However, oligomer with outer spacer n = 8 displays enantiotropic N* and SmC* phases. The temperature range of N* phase for even and odd membered decreased as the outer spacers are increased. The odd–even effect has been found in the I–N* transition temperatures where the odd-parity oligomers exhibit lower values when compared to compounds of an even-parity series. The X-ray diffraction measurements reveal the appearance of SmC* phase that can be associated with the monolayer ordering of these oligomers.     

Order–Disorder Transitions in Model Liquids of Mesogenic Trimers

Monte Carlo simulations have been performed for realistically dense liquids of model trimers consisting of rigid cores connected by virtual bonds representing semiflexible spacers. The conformational characteristics of the trimers are approximately regulated in two cases to mimic (CH₂)_n spacers with n odd or even. All simulated systems undergo reversible isotropic–nematic phase transitions at well defined temperatures, showing odd–even oscillations in good agreement with experiments. The transitions are coupled with a conformational selection favoring extended conformations in the nematic liquids. The odd–even oscillations and the conformational distribution in the nematic liquids are fully explained on the basis of the intrinsic conformational characteristics of the model trimers.     

How do they know? Influencing the relative stereochemistry of the complex units of dinuclear triple-stranded helicate-type complexes

Dinuclear triple-stranded helicates or meso-helicates are formed by self-assembly of linear ligand strands with appropriate metal ions. Very often this self-assembly proceeds with high diastereoselectivity leading either to the helicate or the meso-helicate. The stereoselectivity of the self-assembly process can be influenced by different factors such as the rigidity of the ligand (-->helicate), the number of methylene units in the alkyl spacers (even number of CH2 units --> helicate; odd number --> meso-helicate), template effects, or chiral substituents.     

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.     

Electroluminescent segmented liquid crystalline trimers

The synthesis and liquid crystal behaviour of light‐emitting trimeric liquid crystals consisting of three mesomorphic moieties connected by aliphatic spacers are reported. The combination of an aromatic light‐emitting central core and two cholestanyl (dihydrocholesteryl) groups induces a helical liquid crystalline phase with circularly polarised photoluminescence and electroluminescence. These segmented trimers are designed to possess a high glass transition temperature below which the structure of liquid crystalline phases can be fixed. The effects of odd and even spacers, spacer length and the presence of large lateral substituents on the liquid crystal behaviour and the glass transition temperature of these trimers were studied. Electroluminescence from a segmented liquid crystalline trimer is reported for the first time.     

Correspondence between molecular functionality and crystal structures. Supramolecular chemistry of a family of homologated aminophenols

The crystal structures and packing features of a family of 13 aminophenols, or supraminols, are analyzed and correlated. These compounds are divided into three groups: (a) compounds 1-5 with methylene spacers of the general type HO-C6H4-(CH2)n-C6H4-NH2 (n = 1 to 5) and both OH and NH2 in a para position; (b) compounds 1a, 2a, 2b, 2c, and 3a in which one or more of the methylene linkers in 1 to 3 are exchanged with an S-atom; and (c) compounds 2d, 1b, and 6a prepared with considerations of crystal engineering and where the crystal structures may be anticipated on the basis of structures 1-5,1a, 2a, 2b, 2c, and 3a. These 13 aminols can be described in terms of three major supramolecular synthons based on hydrogen bonding between OH and NH2 groups: the tetrameric loop or square motif, the infinite N(H)O chain, and the beta-As sheet. These three synthons are not completely independent of each other but interrelate, with the structures tending toward the more stable beta-As sheet in some cases. Compounds 1-5 show an alternation in melting points, and compounds with n = even exhibit systematically higher melting points compared to those with n = odd. The alternating melting points are reflected in, and explained by, the alternation in the crystal structures. The n = odd structures tend toward the beta-As sheet as n increases and can be considered as a variable series whereas for n = even, the beta-As sheet is invariably formed constituting a fixed series. Substitution of a methylene group by an isosteric S-atom may causes a change in the crystal structure. These observations are rationalized in terms of geometrical and chemical effects of the functional groups. This study shows that even for compounds with complex crystal structures the packing may be reasonably anticipated provided a sufficient number of examples are available.     

Mesogenic behaviour of p-nitrophenyl group linked with biphenyl mesogens via flexible spacers

Three series of nematogens with a terminal p-nitrophenyl group linked with biphenyl groups via flexible spacers were synthesised and their transitional properties were studied by means of differential scanning calorimetry (DSC) and polarising microscopy (POM). The nematic–isotropic transition temperature and the associated entropy change showed an odd–even effect as the length of the spacers was varied, in which the even members exhibited higher values. Such an odd–even effect was in consistency with the feature of liquid crystal dimers and trimers. On the basis of these data, it seemed reasonable to assume that the terminal p-nitrophenyl group played a role of mesogen in the nematic liquid crystal. The p-nitrophenyl group may work as a mesogen as a result of the interaction with the biphenyl mesogens. The mesogenic behaviour of the terminal p-nitrophenyl group is explained on the basis of neighbouring group effect.