Liquid crystal properties of a mesogenic polyacetylene, poly(11-[(4'-heptoxy-4-biphenylyl)carbonyloxy]-1-undecyne)

The liquid crystalline properties of a mesogenic poly(1-alkyne) and the corresponding monomer were studied using transmission electron microscopy, X-ray diffraction, polarizing optical microscopy and differential scanning calorimetry. The monomer exhibits a monotropic smectic A phase and a metastable crystalline phase. The rigid polymer backbones do not prevent the mesogenic moieties from packing into smectic A and B phases in the temperature ranges 127.6-74.1°C and 74.1°C-room temperature, respectively, on cooling from the isotropic melt.     

Non-linear boomerang-shaped liquid crystals derived from 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole

Boomerang-shaped liquid crystals based on 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP) having a ~ 134° bend in the mesogenic cores were synthesized and their properties investigated by optical microscopy and differential scanning calorimetry. Substituting the nonlinear ODBP mesogenic core with p-dodecyloxyphenyl tails resulted in a non-linear mesogen that exhibited five distinct mesophases and a clearing temperature of 204°C. The highest temperature phase appears to be nematic followed by a smectic C phase. The latter phase in freely suspended films does not appear to exhibit polar order. The highest temperature phase of 4,4'(1,3,4-Oxadiazole-2,5-diyl) di-p-heptylbenzoate shows a schlieren texture with a 2-brush pattern exclusively.     

Non-linear boomerang-shaped liquid crystals derived from 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole

Boomerang-shaped liquid crystals based on 2,5-bis(p-hydroxyphenyl)-1,3,4-oxadiazole (ODBP) having a ~ 134° bend in the mesogenic cores were synthesized and their properties investigated by optical microscopy and differential scanning calorimetry. Substituting the nonlinear ODBP mesogenic core with p-dodecyloxyphenyl tails resulted in a non-linear mesogen that exhibited five distinct mesophases and a clearing temperature of 204°C. The highest temperature phase appears to be nematic followed by a smectic C phase. The latter phase in freely suspended films does not appear to exhibit polar order. The highest temperature phase of 4,4'(1,3,4-Oxadiazole-2,5-diyl) di-p-heptylbenzoate shows a schlieren texture with a 2-brush pattern exclusively.     

Synthesis and evaluation of a series of novel 2-substituted poly(allylalcohol) side chain liquid crystalline oligomers exhibiting ferroelectricity

Abstract

The recently published Baylis-Hillman methodology has been used to prepare a number of side chain liquid crystalline poly(allylalcohols) incorporating a ferroelectric mesogenic side chain. These poly(allylalcohols) exhibited wide range S?_C phases and, in the case of two of these materials, low glass transition temperatures. The transition temperatures and phase behaviour of the SCLC poly(allylalcohols) were compared to acrylate and methacrylate SCLC oligomers containing a similar mesogenic side chain. The response times for two poly(allylalcohols) exhibiting low glass transition temperatures were also measured over a wide temperature range. Although the poly(allylalcohols) had comparable response times to the analogous acrylate and methacrylate SCLCP, they showed the greater temperature dependence of the response time. However, at 39°C one of the SCLC poly(allylalcohols) showed a response time of 65 ms.     

Synthesis and evaluation of a series of novel 2-substituted poly(allylalcohol) side chain liquid crystalline oligomers exhibiting ferroelectricity

The recently published Baylis-Hillman methodology has been used to prepare a number of side chain liquid crystalline poly(allylalcohols) incorporating a ferroelectric mesogenic side chain. These poly(allylalcohols) exhibited wide range S*_C phases and, in the case of two of these materials, low glass transition temperatures. The transition temperatures and phase behaviour of the SCLC poly(allylalcohols) were compared to acrylate and methacrylate SCLC oligomers containing a similar mesogenic side chain. The response times for two poly(allylalcohols) exhibiting low glass transition temperatures were also measured over a wide temperature range. Although the poly(allylalcohols) had comparable response times to the analogous acrylate and methacrylate SCLCP, they showed the greater temperature dependence of the response time. However, at 39°C one of the SCLC poly(allylalcohols) showed a response time of 65 ms.     

Liquid crystalline model compounds based on 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA)

3,3',4,4'-Biphenyltetracarboxylic dianhydride (BPDA) was investigated as the central core unit in mesogenic molecules. Of particular interest was whether the BPDA unit could be self-constrained into a trans-conformation, and thus organize into a liquid crystalline phase. Two homologous series of symmetrical substituted model compounds, 3,3',4,4'-biphenyltetracarboxy-N-N'-bis-(4-n- alkylphenyl) diimides and 3,3',4,4'-biphenyltetracarboxy-N-N'-bis-(4-n- alkoxyphenyl)diimides were synthesized. For both series high temperature smectic A phases were observed. To our knowledge these are the first examples of liquid crystalline behaviour observed with BPDA as the mesogenic core.     

On the structure of binary mixtures of non-symmetric liquid crystal dimers: the alpha-(4-cyanobiphenyl-4-yloxy)-omega(4-alkylanilinebenzylidene-4-oxy) alkanes

Liquid crystal dimers, in which two mesogenic groups are linked by a flexible spacer, exhibit a rich smectic polymorphism for both symmetric and non-symmetric dimers which differ in the nature of the mesogenic groups. For example, smectic phases having monolayer, interdigitated and intercalated structures have been discovered. We have extended our studies of such systems to binary mixtures in an attempt to understand the origin of the different phase structures at the molecular level. The dimers studied include non-symmetric systems differing in the parity of the spacer and in the length of the terminal chains; for comparison we have also studied a mixture of symmetric dimers differing solely in the parity of the spacer. We have constructed the phase diagrams for the various mixtures and found that for certain systems the smectic phases exhibited by either one or both components can be destroyed. To investigate the local structure of the nematic phase for mixtures in which a smectic A phase is eliminated from the phase diagram we have determined their orientational order using NMR and ESR spectroscopy. To provide more direct information on the local structure an X-ray diffraction study was undertaken on certain of the mixtures.     

Mesogenic properties of 1,2,3-tri-[3'-(4'-alkoxyphenyl)-3'-oxo-1'-propenylamino]propane

The properties of compounds incorporating three mesogenic cores linked to a central 1,2,3-trisubstituted propane unit are reported. They form S_A and S_c calamitic liquid crystalline phases with a layer spacing in the orthogonal smectic phase significantly smaller than a single molecular length. The mesogenic properties of related molecules with two mesogenic cores depend on the position of the enaminoketone ring with respect to the joint. Intramolecular dipolar interactions of the enaminoketone rings are suggested as being responsible for the hindered frmation of the trans-conformational structure of the cores in the dimeric molecules.     

On the structure and the chain conformation of side-chain liquid crystal polymers

Abstract

Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R _⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate backbone conformation in the smectic phase is always larger than in the nematic phase. This is attributed to a periodic distribution of the backbone between the mesophase layers. Then, the backbone anisotropy depends not only on the smectic structure (S_A1, S_Ad), but also on the temperature dependence of the density of aligned mesogenic groups in the layers. On the other hand, it is shown that the isotopic mixtures are no longer ideal when polymers deuteriated in the mesogenic moieties are mixed with the corresponding hydrogenous polymers.     

Influence of the mesophase structure on the β-relaxation in liquid crystalline poly(meth)acrylates

The dependence of the rotation of the mesogenic unit around its long axis (β-relaxation) on the actual mesophase in liqid crystalline polymethacrylates and polyacrylates was studied by dielectric spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and in a temperature range from 170 K to 430 K. As mesogenic units derivatives of (p-alkoxy-phenyl)-benzoate were used where different mesophases were achieved by small variation of the mesogenic structure, the spacer length and the tail group of the mesogenic unit. For all samples the temperature dependence of the relaxation rate of the β-relaxation can be described by an Arrhenius equation where both the pre-exponential factor and the activation energy increase significantly with the order of the mesophase. To characterize the structure X-ray measurements were also carried out. The mean lateral mesogenic distance was correlated directly with relaxational quantities.     

A new series of mesogenic derivatives of pyrimidine-substituted

Analogs of known mesogenic 2,5-diarylpyrimidines, 5-[p-alkyl(alkoxy)phenyl]-2-(o-hydroxy-p-alkoxyphenyl)pyrimidines (I), have been synthesized that have a wider mesogenic phase temperature range. Pyrimidines I show smectic C and A phases but not the nematic phase.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 377–381, March, 1992.     

Optically-active comb-branch liquid crystalline polymers having the chiral center in the flexible spacer unit. III. Copolymers of (S)-2-(4′-cyano-4-biphenylyloxy)-1-methylethoxy ethyl methacrylate and di[6-(4-methoxy-4′-oxybiphenyl) hexyl]-2-methylene butane-1,4-dioate

A new series of copolymers with optically-active liquid crystalline side chain units has been synthesized from the comonomers (S)-2-[2-(4′-cyano-4-biphenylyloxy-1-methylethoxy]ethyl methacrylate ( 1 ) and di[6-(4-methoxy-4′-oxybiphenyl)hexyl]-2-methylene butane-1,4-dioate ( 4 ). Chiral nematic phases were exhibited by two members of the series, rich in monomer 1 , while a smectic phase was exhibited in copolymers rich in 4 . While it was thought possible that ordered chiral liquid crystalline phases may be induced by copolymerizing chiral mesogenic monomers with mesogenic derivatives of itaconic acid where the high side chain density encourages greater ordering in the system, no evidence of smectic C^* phases could be found in the present systems. © 1993 John Wiley & Sons, Inc.     

Effect of counter-ion on the thermotropic liquid crystal behaviour of bis(alkyl)-tris(imidazolium salt) compounds

Recently, new thermotropic ionic liquid crystals (LCs) with a hexyl-linked tris(imidazolium bromide) core and two terminal alkyl chains were synthesised and characterised. To explore the effect of different counter-ions on the LC behaviour of this system, derivatives with BF₄^? and Tf₂N^? counter-ions were prepared and analysed. Five of the BF₄^? derivatives were found to exhibit thermotropic LC behaviour. The 12-, 14- and 16-carbon tail BF₄^? compounds form SmA phases. The 18- and 20-carbon tail homologues form what appears to be a smectic phase but are weakly mesogenic and harder to characterise. Only two of the Tf₂N^? derivatives exhibited mesogenic behaviour. The 18-carbon tail Tf₂N^? compound forms an as-yet unidentified, highly periodic smectic phase with positional order while the 20-carbon tail homologue forms a periodic SmA phase. The Tf₂N^? mesogens have much lower clearing points even though their LC phases have more order than the Br^? and BF₄^? mesogens. X-ray diffraction showed that these mesogens have different amounts of tail interdigitation between the smectic layers depending on the counter-ion present. Atomistic molecular dynamics simulations indicated that counter-ion size plays an important role in defining the density of the ionic region, which in turn affects the amount of interdigitation in the smectic phases.     

High hole mobility for a side-chain liquid-crystalline smectic polysiloxane exhibiting a nanosegregated structure with a terthiophene moiety

Side-chain liquid-crystalline siloxane polymers bearing terthiophene moieties as mesogenic pendant groups have been synthesized. An alkenylterthiophene derivative was treated with poly(hydrogenmethylsiloxane) and poly(dimethylsiloxane-co-hydrogenmethylsiloxane)s in Me(2)SiO/MeHSiO ratios of 1:1 and 7:3, respectively, in the presence of the Karstedt catalyst, to produce pale yellow polymers. The degrees of introduction of the mesogenic unit were 100, 50, and 30%, respectively. The polymers exhibit ordered smectic phases at room temperature. The copolymers with dimethylsiloxane units form smectic phases as a consequence of nanosegregation between the mesogenic units and siloxane backbones with the alkylene spacers. Time-of-flight measurement reveals that the hole mobility exceeds 1×10(-2) cm(2) V(-1) s(-1) in the ordered smectic phase of the copolymer with a degree introduction of the mesogenic units of 50%. This value is comparable to that of the highly ordered mesophases of low-molecular-weight derivatives of phenylnaphthalene and terthiophene. Because of the segregation behavior induced by the flexible backbone, a closer molecular packing structure favorable for fast carrier transport may be formed in the smectic phase of the copolymer in spite of the low density of the mesogenic groups.     

A Twist‐Bend Nematic (NTB) Phase of Chiral Materials

New chiral dimers consisting of a rod‐like and cholesterol mesogenic units are reported to form a chiral twist‐bend nematic phase (N_TB*) with heliconical structure. The compressibility of the N_TB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the N_TB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non‐chiral compounds (ca. 10 nm).     

Chiral liquid-crystalline copolyacrylates with biphenyl and phenyl benzoate side groups

The phase behavior and structure of liquid-crystalline phases of three series of copolymers with mesogenic units belonging to the families of biphenyls and phenyl benzoates have been studied, with the former mesogenic units containing a chiral center in a flexible spacer. A variation in the isotropization temperature as a function of composition is well described by the additivity rule, whereas the tilt angle of mesogenic groups in smectic layers changes nonlinearly. This angle decreases beginning from homopolymers and attains the minimum value for the copolymers of the equimolar composition, which show the highest ferroelectric activity among the polymer systems under study.     

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.     

具有氟烷基边链和手性中心液晶化合物的合成及液晶性研究

本文设计合成了十个含氟烷基边链和手性中心的液晶化合物，并通过DSC和偏光显微镜对它们的液晶性进行了研究。其中二环系液晶化合物不显示液晶相或仅显示单边近晶A相。三环系液晶化合物中较长的氟烷基边链有利于近晶相的形成，且当液晶核另一端的烷氧基链的长度适中时，在氟烷基边链和液晶核之间具有手性中心的液晶分子显示了手性近晶C相和其它液晶相。     

Synthesis, structure and characterization of side chain cholesteric liquid crystalline polysiloxanes

A series of liquid crystalline homopolysiloxanes and copolysiloxanes were synthesized. The chemical structures of the monomers M₁-M₇ were confirmed by FTIR and ¹H NMR spectroscopy. The structure-property relationships of the monomers and polymers are discussed; their phase behaviour and optical properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and polarizing optical microscopy. All the monomers, except M₂ and M₇ showed smectic and nematic phases; the copolymers P₈-P₁₅ displayed cholesteric phases. The homopolymers P₁-P₇ exhibited smectic phases. The selective reflection of cholesteric monomers and copolymers shifted to longer wavelengths with increasing length of the rigid mesogenic core, with decreasing length of the flexible spacer, or with increasing content of nematic units. Experimental results demonstrated that a flexible polymer backbone, a rigid mesogenic core and a long flexible spacer tended to produce a lower glass transition temperature, higher thermal stability, and wider mesophase temperature range.     

Novel diphenylacetylene-based room-temperature liquid crystalline molecules with alkylthio groups,and investigation of the role for terminal alkyl chains in mesogenic incidence and tendency

In this study, we offer a new family of alkylthio-containing diphenylacetylene-based liquid crystalline molecules (the so-called tolanes) showing nematic phases stable down to room temperature and high birefringence, with insights into the role for terminal alkyl chains in mesogenic incidence and tendency. A number of asymmetric tolane homologues having various alkyl chain lengths in the alkylthio and alkyl groups at each p-, p’-position were synthesised, and their phase transition behaviour was investigated by polarising optical microscope observation, differential scanning calorimetry and wide-angle X-ray diffraction measurement. Consequently, several homologues exhibited monotropic nematic or highly ordered smectic (soft crystal) phases stable down to room temperature. It is found that a long alkyl group on the side opposite to an alkylthio group is prerequisite for mesogenic incidence. In addition, a nematogenic homologue exhibited a higher birefringence value of 0.20 compared to that of 0.19 for an alkoxy counterpart.