New liquid crystalline di- and tetra-acrylates for network formation

New liquid crystalline diacrylates and tetra-acrylates containing four to six aromatic rings were synthesized and characterized, and their mesophase behaviour was investigated. They are designed to be used in combination with chiral molecules to form cholesteric mesophases which can be crosslinked by photopolymerization. The acrylates presented exhibit broad mesophase ranges since mesogenic moieties longer than three are employed. Most diacrylates show no isotropization, due to premature thermal polymerization above 180°C. Additionally, liquid crystalline dipropionates were synthesized as reference compounds which cannot be crosslinked, and selected examples of these exhibit isotropization temperatures as high as 238°C prior to thermal degradation. Substituents at the mesogenic moiety have a great influence on the mesophase characteristics. Bulky substituents such as the tert-butyl group, induce a nematic mesophase, whereas compounds with small substituents (e.g. OCH3) or unsubstituted molecules also exhibit smectic phases. Tetra-acrylates with unsubstituted and substituted mesogenic units feature nematic mesophases only as a result of the additional spacers attached. Here isotropization was observed without polymerization at temperatures around 120-160°C.     

New liquid crystalline di- and tetra-acrylates for network formation

New liquid crystalline diacrylates and tetra-acrylates containing four to six aromatic rings were synthesized and characterized, and their mesophase behaviour was investigated. They are designed to be used in combination with chiral molecules to form cholesteric mesophases which can be crosslinked by photopolymerization. The acrylates presented exhibit broad mesophase ranges since mesogenic moieties longer than three are employed. Most diacrylates show no isotropization, due to premature thermal polymerization above 180°C. Additionally, liquid crystalline dipropionates were synthesized as reference compounds which cannot be crosslinked, and selected examples of these exhibit isotropization temperatures as high as 238°C prior to thermal degradation. Substituents at the mesogenic moiety have a great influence on the mesophase characteristics. Bulky substituents such as the tert-butyl group, induce a nematic mesophase, whereas compounds with small substituents (e.g. OCH3) or unsubstituted molecules also exhibit smectic phases. Tetra-acrylates with unsubstituted and substituted mesogenic units feature nematic mesophases only as a result of the additional spacers attached. Here isotropization was observed without polymerization at temperatures around 120-160°C.     

Photo- and electro-luminescent properties of thermotropic liquid crystalline quaterphenyl analogues comprising a 2,2'-bi-1,3,4-thiadiazole unit

Thermotropic liquid crystalline quaterphenyl analogues constituting a central 2,2'-bi-1,3,4- thiadiazole ring, the compounds 5,5'-bis(4-methoxy- and 4-octyloxy-phenyl)-1,3,4-thiadiazole, have been prepared and their photoluminescent (PL) and electroluminescent (EL) properties evaluated. The materials form enantiotropic smectic and nematic phases. The PL spectra showed that they emit blue and green fluorescence in the solid state. The octyloxy compound exhibited an EL spectrum with blue emission and is a candidate for organic EL applications.     

Photo- and electro-luminescent properties of thermotropic liquid crystalline quaterphenyl analogues comprising a 2,2'-bi-1,3,4-thiadiazole unit

Thermotropic liquid crystalline quaterphenyl analogues constituting a central 2,2'-bi-1,3,4- thiadiazole ring, the compounds 5,5'-bis(4-methoxy- and 4-octyloxy-phenyl)-1,3,4-thiadiazole, have been prepared and their photoluminescent (PL) and electroluminescent (EL) properties evaluated. The materials form enantiotropic smectic and nematic phases. The PL spectra showed that they emit blue and green fluorescence in the solid state. The octyloxy compound exhibited an EL spectrum with blue emission and is a candidate for organic EL applications.     

Apolar 2-alkoxyalkoxy-substituted nematic liquid crystals

The synthesis is reported of a series of apolar nematic liquid crystals incorporating an alkoxyalkoxy chain attached in a terminal position to the molecular core. The dependence of the mesomorphism and phase transition temperatures on the nature of the terminal chain with one, two or three oxygen atoms was studied. Some compounds with a completely alicyclic molecular core and a terminal 2-methoxyethoxy chain exhibit a nematic phase with a low melting point, birefringence and viscosity and a relatively high clearing point in the absence of smectic phases. They do not to absorb light in the near UV and may be useful as components of UV-stable nematic mixtures for use in photoluminescent liquid crystal displays. The presence of the methoxyethoxy chain leads to a relatively large dipole moment perpendicular to the molecular long axis.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2'-dimethyl-4,4'-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

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.     

Photoluminescent nematic liquid crystalline elastomer actuators

Nematic liquid crystalline elastomer (LCE) actuators possessing both photoluminescent (PL) and stimuli-responsive functions were fabricated and studied. PL-dyes (1-pyrenemethyl acrylate and 4-bromo-2,6-bis-(1?-methyl-benzimidazolyl) pyridine loaded with Eu(III) ion) were synthesised and characterised, and then the dyes were mixed with an acrylate side-on liquid crystalline monomer, a cross-linker and a photo-initiator. Through magnetic field alignment, well-defined LCE micropillar PL actuators were fabricated from the mixed samples by a method combining soft lithography and photo-polymerisation/photo-cross-linking. Microscopic observations indicated that the LCE micropillars showed reversible thermomechanical deformation at the nematic-to-isotropic transition temperature. During the reversible contraction and extension process, the LCE actuator containing 1-pyrenemethyl moieties showed stable photoluminescence, while for the LCE actuator doped with 4-bromo-2,6-bis-(1-methyl-benzimidazolyl)pyridine/Eu(III) complex, the PL emission was quenched at about 100°C, which was before the pillars contraction occurring at a higher temperature. When cooled down to room temperature, the contracted LCE micropillars recovered their original shape and the initial PL emission state. The micron-sized LCE actuators can be used for thermomechanical devices and machines with different PL functions at the same time.     

Morphology of polymer networks polymerized in highly ordered liquid crystalline phases

The morphology and optical properties of polymer stabilized liquid crystals formed in a more highly ordered low molecular weight liquid crystal solvent were studied. Tetrafunctional, mesogenic monomers (with and without flexible spacers) were polymerized in isotropic, nematic and smectic phases of the LC solvent (4′-octyl-4-cyanobiphenyl) and studied with scanning electron microscopy and cross-polarized light microscopy. The network morphology of the nematic and isotropic phase polymerizations showed strong similarities with the corresponding polymerizations in other solvents. Polymerization in the smectic phase, however, resulted in marked increases in network order and directionality. Most dramatically, even the polymer without flexible spacer formed a fibrous network of rodlike units, in contrast to the random, beaded texture formed by the same polymer in nematic or isotropic conditions. Correspondingly, a large increase in birefringence demonstrated significant polymer orientation and more effective orientational interaction with the liquid crystalline solvent.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Abstract

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2′-dimethyl-4,4′-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

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.     

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.     

Thermotropic liquid crystalline polymers containing five-membered heterocyclic groups IX. Synthesis and optical properties of liquid crystalline semi-rigid polyesters composed of a quinquephenyl analogue containing 1,3,4-thiadiazole and aliphatic chains

Novel semi-rigid polyesters containing a quinquephenyl analogue containing 1,3,4-thiadiazole and a central 1,3-phenylene unit in the main chain were synthesized by high temperature solution polycondensation of a dimethyl ester derivative of 1,3-bis(5-phenyl-1,3,4-thiadiazol-2-yl)benzene with an aliphatic (octa-, deca- and dodecamethylene) diol. The proposed structures were confirmed using FTIR and ¹H NMR spectroscopies, and elemental analyses; their liquid crystalline and photoluminescent (PL) properties were examined by means of differential scanning calorimetry, optical texture observations using polarizing microscopy, powder X-ray diffraction, and UV-vis and PL spectra measurements. These measurements showed that the polymers not only show a monotropic solid smectic or disordered crystal phase, but also PL properties with blue emission in HFIP solutions and in the solid phase, Stokes shifts of 116.5-119 nm being observed.     

Thermotropic liquid crystalline polymers containing five-membered heterocyclic groups IX. Synthesis and optical properties of liquid crystalline semi-rigid polyesters composed of a quinquephenyl analogue containing 1,3,4-thiadiazole and aliphatic chains

Novel semi-rigid polyesters containing a quinquephenyl analogue containing 1,3,4-thiadiazole and a central 1,3-phenylene unit in the main chain were synthesized by high temperature solution polycondensation of a dimethyl ester derivative of 1,3-bis(5-phenyl-1,3,4-thiadiazol-2-yl)benzene with an aliphatic (octa-, deca- and dodecamethylene) diol. The proposed structures were confirmed using FTIR and ¹H NMR spectroscopies, and elemental analyses; their liquid crystalline and photoluminescent (PL) properties were examined by means of differential scanning calorimetry, optical texture observations using polarizing microscopy, powder X-ray diffraction, and UV-vis and PL spectra measurements. These measurements showed that the polymers not only show a monotropic solid smectic or disordered crystal phase, but also PL properties with blue emission in HFIP solutions and in the solid phase, Stokes shifts of 116.5–119?nm being observed.     

Thermal recordable novel cholesteric liquid crystalline polyacrylates containing various chiral moieties

To investigate the effect of spacer length and linkages between the rigid mesogenic core and the terminal group on the molecular interaction and physical properties of polymers, two series of novel side chain liquid crystalline polyacrylates were synthesized. These were composed of liquid crystalline monomers with six or eleven methylene segments as spacers, and chiral monomers end capped with menthyl or cholesteryl groups. Liquid crystalline phases of the polymers were investigated using differential scanning calorimetry and polarized optical microscopy, and confirmed with X‐ray diffractometry. Color image recording of the synthesized polymer films was achieved using a thermal treatment, and then fixed by quenching. This investigation demonstrates that the introduction of carbonate linking groups between the rigid mesogenic core and terminal group decreases both the lateral molecular interaction and thermal stability of the liquid crystalline polymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6214–6228, 2008     

Synthesis of novel multi-arm star azobenzene side-chain liquid crystalline copolymers with a hyperbranched core

A series of novel multi-arm star side-chain liquid crystalline (LC) copolymers with hyperbranched core moieties were synthesized by atom transfer radical polymerization (ATRP) using a multi-functional hyperbranched polyether as the initiator and chlorobenzene as the solvent. The multi-functional hyperbranched polyether initiator was prepared from poly(3-ethyl-3-(hydroxymethyl)oxetane) (PEHO) and 2-bromo-2-methylpropionyl bromide. The azobenzene side-chain liquid crystalline arms were designed to have an LC conformation of poly[6-(4-methoxy-4^′-oxy-azobenzene)hexyl methacrylate] with different molecular weights. Their characterization was performed with ¹H NMR, size exclusion chromatograph (SEC), differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM). The multi-arm star side-chain liquid crystalline copolymers exhibited a smectic and a nematic phase, and the phase transition temperatures from the smectic to the nematic phase and from the nematic to isotropic phase increased with increasing the molecular weight of the multi-arm star side-chain liquid crystalline copolymers from 1.78 × 10⁴ to 9.07 × 10⁴.     

Synthesis and characterization of main chain liquid crystalline ionomers containing sulphonate groups

A series of main chain liquid crystalline ionomers containing sulphonate groups pendent to the polymer backbone were synthesized by an interfacial condensation reaction of 4,4'-bis(1,10-sebacyloxo)benzoic acid, brilliant yellow (BY), and 4,4'-biphenyldiol. 4,4'-Bis(1,10-sebacyloxo)benzoic acid exhibited nematic schlieren texture during heating and cooling. The ionomers are thermotropic liquid crystalline polymers and thermally stable to about 270°C. They exhibit broad mesophase regions over a range of 220°C and the same nematic mesomogen with a colourful thread texture as B₀-LCP, which implies that the introduction of an ionic group did not change the texture of the B₀-LCP. However, the thermotropic liquid crystalline properties were somewhat weakened when the concentration of BY was more than 5%. The inherent viscosity in N,N-dimethylformamide solution suggested that intermolecular associations of sulphonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration.     

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P_4M and P_11M) and their mixtures (2?wt?%) in the low molar mass nematogenics 4′-n-pentyl-4-cyanobiphenyl (5CB) and 4′-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A₁ phases were observed for the polyacrylates with four (P_4M) and eleven (P_11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P_4M exhibits an injected smectic phase, whereas P_11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.     

The synthesis and liquid crystal transition temperatures of some weakly polar nematic methyl (E)-[trans-4-substituted-cyclohexyl]-allyl ethers

We have introduced an oxygen atom and a carbon-carbon double bond with a trans-configuration (E) into the terminal alkyl chain of a wide variety of liquid crystalline cyclohexane derivatives to produce a variety of new methyl (E)-allyl ethers. The melting points and tendency to form smectic mesophases are often low, while nearly all of the compounds prepared exhibit a nematic phase. Thus, even two-ring derivatives can exhibit nematic phases over a wide temperature range (≤80°C), sometimes starting below room temperature (T_m≈10°C). Comparisons with the corresponding derivatives incorporating either just an oxygen atom or just a carbon-carbon double bond in the same position indicate that synergetic effects lead to broader nematic phases than would otherwise have been expected. Thus many of the new methyl (E)-allyl ethers exhibit nematic phases over a wider temperature range than the corresponding materials with an unsubstituted alkyl chain attached to the cyclohexyl ring. The new compounds are easily prepared from known starting materials. Many intermediates are themselves liquid crystalline. This allows investigation of the relationship between liquid crystal transition temperatures and the nature of the terminally substituted alkyl chain (for example, incorporating C=C, OH, CO₂C₂H₅ and OCH₃ groups).     

Non-symmetric ether-linked liquid crystalline dimers with a highly polar end group

A new class of non-symmetric dimeric compounds derived from 4-cyano-4′-hydroxybiphenyl in which two rigid parts are connected via flexible spacers have been designed and synthesised. These materials possess trialkoxy chains attached at one end of the molecule, while the other end consists of a biphenyl moiety terminated with the highly polar cyano group. The molecular structures of these dimers have been confirmed by elemental analysis and spectroscopic data and their phase behaviour has been characterised by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Almost all of the synthesised materials exhibit liquid crystalline properties depending on the number of carbon atoms in the terminal chains, where all short chains derivatives form nematic phases and depending on the length of the internal spacer long terminal chains homologues display crystalline or unidentified smectic phase.