Oligo ( p -phenylene)s substituted with long alkoxy chains I. Thermotropic liquid crystalline properties and UV absorption/emission characteristics

A series of linear oligo ( p -phenylene)s containing three, five and seven phenylene groups, modified with short lateral and long terminal alkoxy chains, were synthesized via Palladium complex-catalysed cross-coupling reactions. The thermotropic liquid crystalline and UV absorption/emission properties of these compounds were studied. It was observed that tri ( p -phenylene)s develop a rich mesomorphism including tilted smectic type mesophases (SmC and SmF/SmI) and the nematic phase, whereas penta- and hepta-( p -phenylene)s substituted with short lateral chains develop only the nematic phase. From these observations it is clear that the short lateral chains hinder the layered molecular packing typical of smectic phases and promote the formation of the less ordered liquid-like nematic phase. Mesophases appeared at lower temperatures when longer end chains were used. The optical properties studied by UV-Vis and emission spectroscopy indicate that these systems are promising candidates for blue-emitting layers in electroluminescent devices.     

Liquid crystalline properties of penta(p‐phenylene)s modified with short lateral and long terminal alkoxy chains

A series of penta(p‐phenylene)s modified with short and long alkoxy groups was synthesized via palladium complex‐catalysed cross‐coupling reactions. Molecules substituted with butoxy groups in the central ring showed a nematic phase characterized by a schlieren optical texture, whereas those molecules lacking lateral groups, or substituted with shorter than butoxy groups, did not exhibit liquid crystallinity. Also, it was determined that both the mesophase stability and the clearing point were strongly dependent on the length of the terminal chains. Finally, optical studies of these compounds indicated that the observed light absorption/emission characteristics are independent of the chain lengths.     

Low-temperature nematic phase in asymmetrical 1,3,4-oxadiazole bent-core liquid crystals possessing lateral methoxy group

Asymmetrical bent-core molecules based on 1,3,4-oxadiazole bent-core unit have been synthesised as a new design with a lateral methoxy group at outer phenyl ring of the molecule. These new asymmetrical bent-core molecules resemble hockey-stick shaped due to the presence of two different arms of different lengths. One arm of these molecules is elongated having two phenyl rings and possesses a 4-n-alkyloxy chain of a different number of carbon atoms (n = 4, 8, 12 and 18) and other arm is short and has one phenyl ring with fixed 4-n-octyloxy chain. The bent-core molecules possess a lateral polar methoxy group at the elongated arm of the molecule. These bent-core compounds exhibited fluorescence emission in the UV wavelength region (~377–386 nm) whereas in acetonitrile and dimethylformamide, solvent displays blue emission peak with a large stoke shift.The bent-core molecules with the number of carbon atoms (n = 4, 8 and 12) at the elongated arm exhibited monotropic nematic phase at low temperature, while the 4-n-octadecyloxy chain at the elongated arm displayed smectic A phase. Dielectric studies were performed in the nematic phase of the bent-core mesogens confirm the formation of the cybotactic cluster in the nematic mesophases.     

Azo Monomers Exhibiting Low Layer Shrinkage at the SmA–SmC Transition and trans–cis Light‐Induced Isomerization

Methacrylic monomers containing a (phenylene)azobenzene unit substituted with a lateral cyano group and alkyl chains of different length are synthesized and characterized by NMR techniques. Their liquid‐crystalline properties are studied by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction. All monomers exhibit a mesomorphic behavior that extends over wide temperature ranges with nematic and orthogonal or tilted smectic‐type mesophases, depending on the length of the terminal chain. The smectic structures are determined to be single‐layered with a low layer shrinkage (<5 %) at the SmA–SmC transition. This atypical behavior is attributed to the combination of a high smectic order promoted by both π–π and bond dipole–bond dipole interactions between cyano‐substituted central cores, and a low correlation between neighboring layers arising from dispersive forces between the end groups (methacrylic group and alkyl chain) of the monomer. On the other hand, the trans–cis isomerization of monomers is induced in solution by irradiating with a UV lamp. High cis‐isomer contents (≥96 %) are obtained at the photostationary state, which is reached in a relatively short time (40 s).     

Mesomorphic properties of achiral halogen-substituted banana-shaped compounds

Three banana-shaped achiral compounds, derivatives of 4,6-dichloro-1,3-phenylene bis-[4-(4-n-octyloxyphenyliminomethyl) benzoate], were synthesized by varying the substituent (X = H, F and Cl). Their mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray analysis. The compound with X = H exhibited an enantiomeric nematic phase. The compounds with X = F and Cl formed a nematic phase on heating, while on cooling they formed a nematic phase at high temperature and a smectic A phase at a lower temperature (monotropic). A schematic representation of the mesophase structures for the compound with X = F is also illustrated.     

Determination of elastic constants of a binary system (7CPB+9.CN) showing nematic,induced smectic Ad and re-entrant nematic phases

The temperature variation of the splay and bend elastic constants of a binary system exhibiting nematic-induced smectic A_d and re-entrant nematic phases measured by electric field-induced Freedericksz transition method has been reported. As bend deformation is not permitted in the smectic A phase, bend elastic constant (K₃₃) could only be determined in the nematic and re-entrant nematic phases. In both the nematic phases, the splay elastic constant has the same order of magnitude and does not show any pretransitional effect. However, in the induced smectic A_d phase, the value of K₁₁ is about one to two orders higher than that in the nematic phases. The bend elastic constant shows a strong pretransitional effect near the nematic–smectic and smectic–re-entrant nematic phase transitions. The influence of the presence of the induced smectic phase is observed even in those mixtures which have no induced smectic phases. As the smectic phase is approached, the ratio K₃₃/K₁₁ increases rapidly and diverges to infinity.     

The synthesis and mesomorphic properties of liquid crystals with bulky terminal groups designed for bookshelf geometry ferroelectric mixtures

The synthesis and mesomorphic properties of a systematic range of ortho difluoroterphenyls with a bulky terminal chain are detailed. The bulky terminal chain consists of either a tertiarybutyl group or a trimethylsilyl unit, each separated from the core by a short (dimethylene) chain, with the other terminal chain being either octyloxy or heptyl. The synthesis of the materials was affected efficiently using a combination of low temperature lithiations and palladium-catalysed cross-coupling reactions. Unusually for liquid crystals with bulky terminal chains, the smectic phase stability (particularly smectic C) is upheld by more than the nematic phase stability, and in most cases the smectic C phase stability is actually higher than comparable analogues with conventional unbranched terminal chains. It is postulated that the surprisingly high smectic C phase stability results from a phase separation effect due to the incompatibility of the spherical bulky group and the conventional unbranched terminal chain, hence implying that the smectic ‘layers’ are well defined, and such definition of the layers bodes well for bookshelf geometry in ferroelectric mixtures.     

Synthesis,phase transitions and birefringence of novel liquid crystalline 1,4-phenylene bis(4-alkylthio benzoates) and insights into the cybotactic nematic behaviour

We synthesised a novel family of liquid crystalline 1,4-phenylene bis(4-alkylthio benzoates), of which homologues with different alkyl chain lengths of 1–8 were designed, to investigate the structure–property relationship. The mesogenic incidence and tendency were found to be strongly dependent on the carbon numbers in the terminal alkyl chains. Even members formed widely monotropic or enantiotropic nematic (N) phases compared to odd members that showed either none or monotropic-narrower ones. The temperature dependence of birefringence (Δn) for the hexylthio homologue was evaluated and compared to that for a hexyloxy counterpart. It was found that the hexylthio homologue exhibited higher Δn values than the hexyloxy counterpart over the entire range of near T_IN–T. In addition, wide-angle X-ray diffraction measurements, using magnetically aligned specimens, found enhanced cybotactic nematic tendency with smectic (Sm) A-like temperature dependence for the hexylthio analogue, due to the intermolecular attractive S···S interaction, in comparison with the hexyloxy analogue exhibiting N phase with clear Sm C-type clusters. We revealed the actual benefits of alkylthio groups in the fluid N phase.     

Liquid crystalline conjugated polymers and their applications in organic electronics

This article describes the syntheses and electro‐optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p‐phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p‐phenylenevinylene)s, the Suzuki‐ or Yamamoto‐coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main‐chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side‐chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field‐effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo‐fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713–2733, 2009     

Chiral and orientationally ordered fluid mesophases formed by oxadiazole bisaniline based achiral bent mesogens

Development of new liquid crystalline materials exhibiting interesting properties and phases continues to be an enabling enterprise in the forward march of their successful display and non-display applications. The design and synthesis of a homologous series of liquid crystalline bent-core compounds derived from the oxadiazole bisaniline moiety and the phase behavior of three members of the series that exhibit nematic, smectic C, and dark conglomerate phases is reported. The liquid crystalline phases exhibited by these mesogens are characterized using polarized optical microscopy, differential scanning calorimetry and x-ray scattering techniques. All three homologs prepared exhibit the nematic phase. Interestingly, the homolog with short hexyl terminal chains exhibits only the nematic phase that is stable over a very broad, nearly 100 K wide, temperature range. The compound with terminal octyl chains shows the chiral dark conglomerate phase below the nematic phase despite the bent molecules being achiral. The homolog with dodecyl alkyl chains is found to possess the smectic-C and two additional lamellar phases besides the nematic phase. These compounds enrich the library of achiral bent-core materials capable of exhibiting chiral and nematic phases.     

Ferroelectric smectic meso-phase formed by banana-shaped achiral liquid crystals

A new banana-shaped achiral molecule, 1,3-phenylene bis[4-(3-chloro-4-n-octyloxyphenyliminomethyl)benzoate] (PBCOB) has been synthesized, and its ferroelectric properties and homeotropic alignment investigated. The presence of a lateral chloro-substituent in the Schiff 's base moiety prevents the regular stacking of molecules and results in lowering the transition temperature and the degree of crystallinity of the switchable banana phase. Their smectic mesophases, including a switchable banana phase B₇, were characterized by differential scanning calorimetry, X-ray scattering and polarizing optical microscopy. Both the left- and right-handed helical domains are spontaneously formed upon cooling from the isotropic liquid to the switchable banana phase B₇. By X-ray study, the smectic phases showed a layer spacing of 38.1 Å, compatible with the end-to-end distance of the molecule with a bent conformation. Significantly, the smectic B7 phase exhibited a periodicity of 292 Å that corresponds to a helical structure with periodicity about 7.5 times 38.1 Å. The spontaneous polarization for PBCOB is about 50 nCcm^-2 and shows a temperature dependence. The ferroelectric lyomesophase of PBCOB showed a ferroelectric electro-optical switching range extending more than 50°C, switchable at room temperature.     

Dielectric properties of three‐ring fluorinated compounds

Four three‐ring compounds, consisting of two cyclohexyl rings and one mono‐ or difluorinated phenyl ring, were studied using dielectric spectroscopy methods over a broad frequency range (1 kHz–3 GHz). They exhibit a nematic phase in a broad temperature interval, enriched by a smectic B phase in one case. The static and dynamic dielectric properties were analysed. It was established that the bridging CH₂CH₂ group placed between cyclohexyl and phenyl rings considerably changes the reference frame of the molecule, unlike the situation when it links two cyclohexyl rings. In the nematic and smectic B phases the motion around the short axis is a Debye process, whereas the rotation around the long axis is split into two processes: independent rotation of the whole molecule and its fluorophenyl part.     

Synthesis and phase behaviour of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

The homologous series of side chain liquid crystal polymers, the poly[ω-(4-methoxyazobenzene-4′-oxy)alkyl methacrylate]s, has been prepared in which the length of the flexible alkyl spacer has been varied from 3 to 11 methylene units. All the polymers exhibit liquid crystalline behaviour. The propyl and butyl members show exclusively nematic behaviour. The pentyl, hexyl, octyl and decyl members show a nematic and a smectic A phase while the heptyl, nonyl and undecyl homologues exhibit only a smectic A phase. The smectic A phase has been studied using X-ray diffraction and assigned as a smectic A₁ phase in which the side chains are fully overlapped and the backbones are confined to lie between the smectic layers. For the nonyl member an incommensurate smectic phase is observed. The dependence of the transition temperatures on the length of the flexible spacer is understood in terms of the average shapes of the side chains.     

Studies on thermotropic liquid-crystalline polymers: Part X. Synthesis and properties of crosslinkable aromatic copoly(ester)s containing conjugated double bonds

A series of aromatic copoly(ester)s containing conjugated double bonds was prepared from p-phenylene bis(acrylic acid) (PPBA) with a mixture of methylhydroquinone (MHQ) and various hydroxycarboxylic acids in the presence of diphenylchlorophosphate (DPCP) and pyridine as a catalyst and solvent. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC) and thermal optical polarized microscopy. Under an optical polarized microscope all copoly(ester)s show a nematic thermotropic liquidcrystalline phase. Upon heating, these polymers undergo a photocrosslinking reaction characterized by IR and solubility analysis. This crosslinking reaction also takes place in the liquid-crystalline phase with the retention of the nematic order in the final crosslinked solid. © 1993 John Wiley & Sons, Inc.     

New liquid‐crystalline poly(ester amide)s: The role of nitro groups in the phase behavior

New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004     

Preliminary Communication : Induction of smectic A phases by electron donor-acceptor interaction between calamitic mesogens and 2,4,7-trinitrofluorenone

The mesomorphic properties of conventional rod-like liquid crystals (diphenyl1,3,4-thiadiazoles, diphenylpyrimidines, diphenyltriazines, diphenyltetrazines and p-terphenyl derivatives), of macrocyclic liquid crystals and of dimesogens can be influenced by addition of the electron acceptor 2,4,7-trinitrofluorenone (TNF). Thereby nematic and smectic C phases are suppressed and smectic A phases can be stabilized or induced. Long and branched terminal chains result in a strong stabilization of the SA phase, whereas no smectic phase is induced to accompany the nematic phases of mesogens with short terminal chains.     

新型含氧亚甲基和亚胺桥键的液晶化合物的合成及介晶性

报道一类新的、结构通式为MeO₂CC₆H₄CH₂OC₆H₄CH＝NC₆H₄Y, Y＝OC_nH_2n＋1, Me, Cl, Br, NO₂, H 的棒状液晶化合物的合成. 通过DSC和偏光显微镜对其介晶性研究发现, 除Y＝H外, 这些化合物均具有介晶性. 当Y为非烷氧基时, 呈向列相液晶; 当Y为较短的烷氧基时(n＝1～3), 液晶化合物具有向列相(N); Y为较长烷氧基时(n＝4～16 ), 液晶化合物只有近晶B相(S_B)和近晶A相(S_A); S_A-I相变的熵变随烷氧链原子数而奇-偶变化, 但与N-I相变的“奇-偶效应”相反.     

Studies on the thermotropic liquid-crystalline polymer. VIII. Synthesis and properties of fully aromatic poly(ester)s and poly(amide-ester)s containing p-phenylene diacrylic group

Three series of polymers containing p-phenylene diacrylic group were prepared by direct polycondensation in the presence of diphenylchlorophosphate and pyridine. Series I was prepared from p-phenylene bis(acrylic acid) with various hydroquinones. Series II was prepared from p-phenylene bis (β-cyano acrylic acid) with methylhydroquinone. Series III was prepared from 3-methyl-4-aminophenol with p-phenylene bis(acrylic acid) or p-phenylene bis(β-cyano acrylic acid), respectively. The phase behavior of these polymers was studied by differential scanning calorimetry (DSC), optical polarizing microscopy equipped with a heating stage, and wide-angle x-ray diffraction (WAXD). It was found that these polymers, except IIIb , exhibit thermotropic liquid-crystalline properties and show threaded or Schlieren texture under the optical polarizing microscopic observation. Furthermore, the melting temperatures of these polymers were decreased in the range of 254–354°C by incorporating with p-phenylene diacrylic group into the main chain. © 1993 John Wiley & Sons, Inc.     

Molecular dynamics and ordering of side chain liquid crystal polymers as studied by paramagnetic resonance

Abstract

Molecular dynamics of side chain liquid crystalline polymers (LCP) and their components were studied using the technique of paramagnetic resonance. A cigar shape spin probe (COL) and a nearly spherical spin probe (TPL) were used to study the motions and order of the LCPs. Computer simulations of the observed spectra were performed. Both rotational correlation times and order parameters were extracted from these simulations. We found that LCPs containing 30 per cent and 50 per cent of mesogenic side chains had about the same viscosity as indicated by nearly equal tumbling times at the same temperature. In addition, the LCPs motion is considerably slower than that of the monomeric liquid crystal indicating that the spacer couples the motions of the side chains to those of the main chain. Rotations about axes perpendicular to the side chain are slowed more than rotations about an axis parallel to the side chain. DSC measurements were employed to study the phase transitions. The 30 and 50 per cent LCPs displayed first order NS_A transitions, but the 50 per cent LCPs transition was much weaker, in agreement with McMillan's theory which predicts a first order transition for T _NS/T _NI>0.87 (observed ratios are 0.98, 0.90 and 0.86 for 30, 50 and 100 per cent LCPs, respectively). The 30 per cent LCP has a very short nematic range so that the nematic order, which is not saturated at the NS transition, can couple with the smectic order. This was indicated by a sharp change in slope of the order parameter versus temperature plot as the smectic is entered. The LCPs studied formed a highly ordered glass when cooled in a 1 T field. If one could find a LCP with similar ordering properties whose glass temperature is well above room temperature, then one would have a useful binder for the manufacture of haze-free polymer dispersed liquid crystal displays.     

Bromine-terminated azobenzene liquid crystals

A series of liquid crystals (LCs) of bromine-terminated azobenzene were synthesised and characterised. The LCs were composed of an azobenzene core, an alkyl chain and a flexible spacer with a bromine atom at a remote position. Mesomorphic properties were dependent on both the alkyl chain length and the relative position of the bromine atom at the end of the spacer group. The nematic phase was favoured over the smectic A phase for alkyl chains with one and seven carbon atoms. However, the SmA mesophase was dominant for compounds with 10-carbon alkyl chains. The remote bromine atom in the spacer group favoured SmA for homologous with n-decyl chains and the nematic phase for n-heptyl and methyl groups. Molecular modelling showed that the azobenzene LCs tended to adopt the all trans-conformation in the gas phase as the number of carbon atoms increased. For short spacer groups, bent conformations contributed to the level population proportion of conformers. For the non-LC 5a, the gauche conformation became the most stable with a torsional angle of –68.9°. X-ray experiments showed a monolamellar SmA mesophase in an antiparallel arrangement. Absorption maxima at 360 and 440 nm were assigned to π–π* and n–π* transitions, respectively.