Preparation and properties of laterally multifluorinated benzoxazole-based nematic mesogens

Series of laterally multifluorinated heterocyclic compounds, 2-(2?,3-difluoro-4?-alkoxy-1,1?-biphenyl-4-yl)-benzoxazole derivatives (nPF(2)PF(3)Bx), are prepared and characterised. They mainly display enantiotropic nematic mesophases with wider mesophase ranges of 12–107°C (heating process) and 22–134°C (cooling process) than the corresponding analogues. The enhanced nematic mesophase stability is achieved via slightly increasing inter-ring twist angle with inter-ring lateral fluorine substitute in biphenyl unit, as well as through improving the molecular polarity with multifluorine substitutes. Meanwhile, two inter-ring lateral fluorine atoms lead to a decrease in melting/clearing points and a wide nematic mesophase range, which makes it possible for heterocyclic mesogens nPF(2)PF(3)Bx to use in nematic liquid crystal display mixtures.     

Preparation and properties of lateral monofluoro-substituted benzoxazole-based mesogenic compounds

A series of 2-(3?-fluoro-4?-alkoxy-1,1?-biphenyl-4-yl)-benzoxazole liquid crystals (coded as nPF(3)PBx) were prepared, where a lateral fluorine substituent, as well as methyl, chlorine and nitro terminal groups, was introduced into the molecules to investigate the effects of different polar substituents on the liquid crystal properties. The mesomorphic and photophysical properties were investigated. The results show that compounds nPF(3)PBx have enantiotropic mesophases; meanwhile, they exhibit UV–vis absorption bands with maxima at 323–326 nm and photoluminescence emission peaks at 389–395 nm, respectively. It is noted that nPF(3)PBx with terminal polar groups or electron-withdrawing groups (NO₂, Cl) display higher clearing temperatures and wider mesophase range than those of the corresponding homologues with terminal non-polar groups or electron-donating groups (CH₃, H). Meanwhile, compared with two lateral fluorine-substituted analogues containing 3,5-difluorophenyl unit, lateral monofluoro-substituted nPF(3)PBx display enhanced mesophase range both in heating and cooling except for terminal methyl-substituted compounds, as well as show obvious red-shifted UV–vis absorption bands and photoluminescence emission, which are attributed to the enhanced dipole–dipole interaction caused by increased dipole moment.     

Improved nematic mesophase stability of benzoxazole-liquid crystals via modification of inter-ring twist angle of biphenyl unit

A series of nematic heterocyclic liquid crystals, 2-(2?-fluoro-4?-alkoxy-1,1?-biphenyl-4-yl)-benzoxazole derivatives (coded as nPF(2)PBx) bearing hydrogen (nPF(2)PBH), methyl (nPF(2)PBM) and nitro (nPF(2)PBN) terminal groups, respectively, are developped and investigated. The results show that the nematic mesophase stability is obviously improved via a slightly increase in the inter-ring twist angle between the planes of two phenyl rings in the biphenyl unit, where modification of the twist angle can be achieved by adjusting the position of the lateral monofluorine substituent from the outer to the inter ring of the biphenyl mesogenic core unit. Meanwhile, the inter-ring lateral fluorine substituent results in a decrease in both melting and clearing points but only a nematic mesophase with an acceptably wide mesophase range for nPF(2)PBx, and thus a potential application in liquid crystal display mixtures is expected, especially for the compounds nPF(2)PBM and nPF(2)PBN. The reduced π–π interaction/conjugation caused by the increased twist angle is considered as one of the possible reasons for the formation of a nematic mesophase.     

Synthesis and characterisation of benzoxazole-based liquid crystals possessing 3,5-difluorophenyl unit

Series of fluorinated compounds, 2-(3′,5′-difluoro-4′-alkoxybiphenyl-4-yl)-benzoxazole derivatives (nFBx), were prepared and characterised. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. In the case of carbon atoms in the alkoxy chain between 4 and 10, they exhibited enantiotropic mesophases with the mesophase ranges of 12–119°C and 23–152°C on heating and cooling for compounds bearing different substituents (H, CH₃, Cl, and NO₂). With the exception of nitro-substituted compounds, the nFBx series displayed intense photoluminescence emission at 380–385 nm in methylene chloride solution when they were excited at their absorption maxima. Compared to non-fluorinated analogues, fluorinated compounds nFBx (apart from nitro-substituted compounds) exhibited much lower melting points, but comparable or slightly narrower mesophase ranges during both heating and cooling, which were attributed to the disruption of the side-to-side intermolecular packing caused by the two lateral fluoro substituents.     

Preparation and mesomorphic properties of 1-methyl-1H-benzimidazole-based compounds

A series of 1-methyl-1H-benzimidazole-based compounds, 2-(4?-alkoxy-1,1?-biphenyl-4-yl)-1-methyl- 1H-1,3-benzimidazole derivatives (nPPMx-M) with terminal hydrogen, methyl and nitro moieties (coded as nPPMH-M, nPPMM-M and nPPMN-M, respectively), were prepared and their structures were characterised. The compounds display enantiotropic smectic mesophases for hydrogen and methyl terminated compounds (nPPMH-M and nPPMM-M), and enantiotropic nematic mesophases for nitro terminated compounds (nPPMN-M) with short alkoxy chain below than 10 carbon atoms, where the mesophase ranges are 24–72°C and 74–104°C on heating and cooling processes for nPPMH-M, 90–119°C and 110–135°C for nPPMM-M, and 102–129°C and 113–207°C for nPPMN-M, respectively. It is noted that the compounds nPPMx-M exhibit much lower melting points and much wider mesophase range both in heating and cooling than non-1-methyl substituted analogs, which are ascribed to the disruption of hydrogen bonding among the molecules caused by methyl substitution at 1-position of benzimidazole. Meanwhile, among the compounds nPPMx-M, much wider mesophase ranges are obtained for nPPMM-M and nPPMN-M, indicating a much high mesophase stability for the compounds bearing terminal moiety (CH₃ and NO₂).     

Synthesis and mesomorphic properties of the nematic mesophase benzoxazole derivatives with big twist angle of difluoro-biphenyl unit

Modifying the position and numbers of lateral fluorine substituent is a common method to design and adjust the mesophase of liquid crystal compounds. Here, a series of 2-(2,2?-difluoro-4?-alkoxy-1,1?-biphenyl-4-yl)-5-substituted benzoxazole with both non-polar (H, CH₃) and polar (NO₂) groups (coded as nPF(2)PF(2)Bx) is synthesised and characterised. All of the compounds show a conspicuous inter-ring twist angle of 38° compared with corresponding reference compounds I and II which are calculated by density functional theory method, and it is interesting to note that the final compounds nPF(2)PF(2)Bx show only nematic mesophase during heating or cooling. Meanwhile, the UV-vis absorption bands and photoluminescence emission peaks both display remarkable blue-shifted. The aforementioned results reveal that lateral difluoro substituents play a key role to stable the nematic mesophase by increasing the dihedral angle of biphenyl.     

Phase transition of syndiotactic polypropylene in electrospun nanofibers during progressive heating

By means of high-temperature electrospinning process, syndiotactic polypropylene (sPP) nanofibers with an average diameter of 127 nm were obtained using a rotating disc as a collector. The aligned fibers were subjected to progressive heating for fiber melting. During heating, structural evolution of the sPP nanofibers was investigated in situ by means of two-dimensional wide-angle and small-angle X-ray scattering with synchrotron radiation sources. It was found that the as-spun fibers consist of the antichiral form I (9 %), mesophase (31 %), and amorphous phase (60 %), in the absence of isochiral form II. Upon heating, the mesophase started to melt and completely disappeared at 90 °C. The melting of the mesophase directly produced amorphous chains at 35–60 °C, and brought up the isochiral form II at low temperatures (60–70 °C), as well as the antichiral form I at high temperatures (70–110 °C). These events were in accordance with the DSC heating curve, which exhibited a small endotherm centered at 52 °C for the mesophase melting, followed by a shallow and broad exotherm associated with two phase-transition events, i.e., the crystal reorganization and the crystallization of supercooled liquid. The former is likely due to the solid–solid transition of meso→II phase as suggested by Lotz et al. (Macromolecules 31:9253, 1998), and the latter is relevant with crystallization of amorphous chains to develop the thermodynamic stable form I phase at high temperatures.     

Synthesis and study the liquid crystalline properties of compounds containing benzoxazole core and terminal vinyl group

Terminal vinyl-based benzoxazole liquid crystalline compounds, 2-(3-fluoro-4?-alkoxy-1,1?-biphenyl ?4-yl)-5-(2-propenyloxymethyl)-benzoxazole (nPPF(2)BP), were synthesised and their structures were confirmed by infrared (IR) spectra, proton nuclear magnetic resonance (¹H-NMR) spectra, gas chromatography with electron impact-mass spectrometry (GC/EI-MS), matrix-assisted laser desorption/ionisation-time of flight (MALDI-TOF) mass spectrometry and elemental analysis (EA). The compounds show enantiotropic smectic/nematic phases with mesophase ranges are 71–97 °C and 87–136°C on heating and cooling processes for nPPF(2)BP, respectively. They give low melting points due to lateral fluoro substituent and flexible terminal 2-propenyloxymethyl chain. It is found that the compounds nPPF(2)BP with shorter alkoxy chain (n = 3, 4) exhibit a wide range of nematic mesophase, which is ascribed to enhanced π–π interaction caused by terminal vinyl moiety, whereas further elongation of the terminal alkoxy chain results in supressing nematic phase and increasing smectic mesophase. Compared with methyl terminated analogues, 2-propenyloxymethyl terminated compounds nPPF(2)BP display much lower melting points and wider or comparable mesophase range both in heating and cooling.     

Nematic mesophase enhanced via lateral monofluorine substitution on benzoxazole-liquid crystals

Fluorine is widely used as a lateral substituent to modify the physical properties of liquid crystals. Here, laterally monofluorinated compounds, 2-(4?-alkoxy-2-fluorobiphenyl-4-yl)-benzoxazole derivatives (nPPF(2)Bx) bearing different substituents (H, CH₃, NO₂, coded as nPPF(2)BH, nPPF(2)BM and nPPF(2)BN, respectively) at 5-position, were synthesised and characterised. It is interesting to note that these only display enantiotropic nematic mesophases with mesophase ranges of 12–28°C and 13–45°C on heating and cooling for nPPF(2)BH, 46–97°C and 62–120°C for nPPF(2)BM and 82–108°C and 87–113°C for nPPF(2)BN, which are very different from the corresponding monofluorine-substituted analogue (compounds I) with enantiotropic smectic or smectic/nematic mesophases. The enhanced nematic mesophase is attributed to the reduced π–π interaction/conjugation resulting from the twisted structure of the molecule caused by the introduction of a fluorine atom into the inter-ring of the biphenyl unit. These results suggest that modification of the monofluorine substituent position is an effective method to improve the nematic mesophase in benzoxazole-liquid crystals.     

Synthesis and Characterization of Achiral Bent‐Core Liquid Crystalline Molecules Containing Salicylaldimine‐Based with a Wide Temperature Range of SmCP Phase

The design and synthesis of a series bent‐core materials base on a 3,4′‐biphenyldiol central core containing salicylaldimine‐based and two terminal tetradecyloxy tails are reported. In addition, the effects of lateral substituents (R = F and Cl) at the biphenyl core into 3′‐position are examined. These substituents have a strong influence in reducing the clearing temperatures and increasing temperature range of SmCP phase. Upon cooling process the isotropic liquid, compound SB‐Cl exhibits the lowest clearing transition temperature of 180°C and the widest SmCP phase range of 129°C. The mesophase behaviour were investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and electro‐optical (EO) measurements in the mesophase temperature range.     

Synthesis and properties of mesogenic laterally fluorinated compounds containing benzoxazole unit

Series of mesogenic laterally fluorinated compounds, 2-(2′,3′-difluoro-4′-alkoxybiphenyl-4-yl)-benzoxazole derivatives (nB-Fx) bearing different substituents (H, CH₃, Cl, NO₂, coded as nB-FH, nB-FM, nB-FC and nB-FN, respectively) at 5-position, were prepared and characterised. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. nB-Fx with alkoxy chain lengths of 2 to 10 carbons exhibited enantiotropic mesophases, for which the mesophase ranges were 0°C–58°C and 0°C–71°C on heating and cooling for nB-FH, 41°C–93°C and 66°C–140°C for nB-FM, 44°C–133°C and 87°C–155°C for nB-FC, and 0°C–76°C and 0°C–95°C for nB-FN, respectively. Compared to non-fluorinated analogues, with the exception of nB-FC, fluorinated nB-Fx mainly exhibited nematic mesophase both in heating and cooling, which were attributed to the disruption of the side-to-side intermolecular packing caused by the two ortho-lateral fluoro substituents. For nB-Fx series, nB-FM, nB-FC and nB-FN exhibited a much wider mesophase range than the corresponding nB-FH series, which indicated that the substituent at benzoxazole moiety was helpful in increasing the mesophase stability. With the exception of nB-FN, the nB-Fx series displayed intense photoluminescence emission at 379–383 nm in methylene chloride solution, when it was excited at its absorption maxima.     

The effect of terminal substituents on crystal structure,mesophase behaviour and optical property of azo-ester linked materials

A series of azo-ester linked mesogen containing liquid crystalline acrylate compounds C1-C6 having different terminal groups (–F, –Cl, –Br, –OCH₃, –OC₂H₅ and –OC₃H₇) were successfully synthesised and characterised. The chemical structure, purity, thermal stability, mesophase behaviour and optical property of the synthesised compounds were investigated by different instrumental techniques. X-ray crystal structure showed that compounds C1, C4 and C5 exhibited more stable E configuration with two bulky group in the opposite side of the N=N double bond motifs. The fluoro-substituted derivative (C1) is connected by the R¹₂(5) type of C–H…O hydrogen bond motifs whereas the molecules of C4, and C5 are connected to each other by means cyclic R²₂(8) type of C–H…O hydrogen bond motifs. Thermogravimetric study revealed that the investigated compounds exhibited excellent thermal stability. All the compounds showed enantiotropic liquid crystal (LC) phase behaviour and the mesophase formation was greatly influenced by the terminal substituents. Alkoxy (–OCH₃, –OC₂H₅ and –OC₃H₇) substituted compounds exhibited greater mesophase stability than those of halogen (–F, –Cl and –Br) terminated derivatives. UV-vis spectroscopic study revealed that the investigated compounds exhibited a broad absorption band around 300–420 nm with absorption maximum (λ_max) of nearly 370 nm.     

Preparation and characterisation of laterally monofluorinated mesogenic benzimidazole-based compounds

Series of laterally monofluorinated compounds, 2-(4?-alkoxy-3-fluorobiphenyl-4-yl)-1H-benzimidazole derivatives (nPPF(3)Mx) bearing different substituents (H, CH₃, NO₂, coded as nPPF(3)MH, nPPF(3)MM and nPPF(3)MN, respectively) at 5-position, were prepared and their structures were characterised. According to the results from differential scanning calorimetry and polarising optical microscopy, the present compounds nPPF(3)Mx exhibit enantiotropic smectic mesophases, for which the mesophase ranges are 13–67 and 47–111°C on heating and cooling for nPPF(3)MH, 84–112 and 126–154°C for nPPF(3)MM, and 23–102 and 49–117°C for nPPF(3)MN, respectively. Compared to non-fluorinated analogues, monofluorinated nPPF(3)Mx have low melting/clearing points and display enhanced mesophase range both in heating and cooling, which are attributed to the disruption of the side-to-side intermolecular packing caused by the ortho lateral fluoro substituents and the increased dipole–dipole interaction between the polar fluoro-substituted molecules, respectively. It is noted that nPPF(3)MM and nPPF(3)MN show a much wider mesophase range than nPPF(3)MH, which suggest that the substituent at benzimidazole moiety can improve the mesophase stability.     

Effect of lateral bromo substituent on the phase behavior of four-ring azo/ester/azo liquid crystalline materials

ABSTRACT

In order to study the influence of lateral Br substitution on mesophase behaviour, five homologous series of 4-substituted phenylazo phenyl 4?-(3?-bromo-4?-alkoxyphenylazo) benzoates (In_a–e) have been synthesised. Within each homologous series, the alkoxy group varies from 6 to 16 carbons, while other terminal group substituents, X, are CH₃O, CH₃, H, Br and NO₂ groups; the mesophase behaviour of these series is compared with previously prepared laterally neat analogues, 4-substituted phenylazo phenyl 4?-(4?-alkoxyphenylazo) benzoates (IIn_a–e) and laterally methyl analogues, 4-substituted phenylazo phenyl 4?-(3?-methyl-4?-alkoxyphenylazo) benzoates (IIIn_a–e). Similar to lateral methyl analogues, the present series, lateral Br substitution showed that, independent of the polarity of the substituent X or the alkoxy-chain length, the nematic phase is predominant with relatively high stability and broad temperature ranges. The mesophase stability varies between 204.0°C and 335.0°C for the nematic phase and 169.6°C and 281.0°C for the SmA phase. Their total mesophase temperature ranges vary between 87.2°C and 201.4°C. All compounds were found to be thermally stable within the mesophase temperature range, except the lower homologue of the nitro and Br substituted derivatives. The obtained results are discussed in terms of molecular polarisability.     

Synthesis and liquid crystalline properties of substituted 2,5‐diaryl 1,3,4‐oxadiazole derivatives without flexible chains

A series of new compounds based on aromatically 2,5‐disubstituted 1,3,4‐oxadiazoles without flexible chains, formulated as p‐R–C₆H₄–(OC₂N₂)–(p‐C₆H₄)₂–R′ with (i) R = CH₃O, R′ = CH₃O, CH₃S, F, H (Ia–Id), (ii) R = CH₃S, R′ = CH₃O, CH₃S, F, H (IIa–IId) and (iii) R = F, R′ = CH₃O, CH₃S, F, H (IIIa–IIId) (p‐C₆H₄ and OC₂N₂ represent a p‐phenylene spacer and a 1,3,4‐oxadiazole ring, respectively), were synthesised and characterised by ¹H and ¹³C NMR, MS and HRMS techniques. Mesomorphic properties were investigated using differential scanning calorimetry and polarizing optical microscopy. All of the target compounds (except Id, IId, IIIc and IIId) exhibited an enantiotropic nematic mesophase with high melting temperatures. The liquid crystalline properties of these compounds were influenced greatly by polarity, steric factors and positions of the terminal groups. The effect of the terminal groups on the liquid crystal properties is discussed.     

Phase behavior and structure in mesogen containing polyurethanes

The mesophase to crystal phase transition observed upon heating the monotropic liquid crystal polyurethane (2,6-LCPU-6), based on the mesogenic biphenol 4,4′-bis(6-hydroxyhexoxy)biphenyl (BHHBP) and 2,6-toluenediisocyanate (2,6-TDI), has been investigated by differential scanning calorimetry (DSC), wide angle x-ray scattering (WAXS) and infrared (IR) spectroscopy. Hexafluoroisopropanol (HFIP) fast solvent-evaporation casting resulted in 2,6-LCPU-6 thin films with a glassy mesophase morphology. The mesophase to crystal exothermic transition has been observed by DSC between 130 and 140°C, depending on sample preparation. It is accompanied by a substantial increase of H-bonding between urethane C=O and N-H, as observed by IR. Curve fitting analysis of the conformationally sensitive amide I region revealed three bands; ordered H-bonded carbonyl groups, disordered H-bonded carbonyl groups, and “free” carbonyl groups. The prime feature of the 130°C transition is the substantial increase of ordered H-bonded carbonyl groups at the expense of disordered H-bonded carbonyl groups. Crystal melting occurs between 180 and 210°C and is accompanied by the complete disappearance of the ordered H-bonded peak along with substantial changes in the frequency and width at half-height of the disordered H-bonded peak     

Tolane liquid crystals bearing fluorinated terminal group and their mid-wave infrared properties

This paper describes the synthesis and characterisation of several liquid crystal (LC) compounds having a tolane core structure and a trifluoromethoxy terminal group. The mesomorphic properties, mid-wave infrared (IR) absorption and birefringence were investigated. These materials exhibit low absorption in mid-wave IR regions (MWIR) and high birefringence (Δn ~ 0.26–0.29). The impact of fluorine substitution was investigated. Compounds with monofluorine exhibit wide mesophase temperature (88.5°C), and the mesomorphic behaviour weakened with increasing fluorine atom. The results show that they are promising LC materials for applications in the MWIR.     

Substituent effect on azobenzene‐based liquid‐crystalline organophosphorus polymers

An Erratum has been published for this article in Journal of Polymer Science Part A: Polymer Chemistry (2003) 41(23) 3862 A new series of combined‐type, azobenzene‐based organophosphorus liquid‐crystalline polymers were synthesized, and their photoisomerization properties were studied. The prepared polymers contained azobenzene units as both the main‐chain and side‐chain mesogens. Various groups were substituted in the terminal of the side‐chain azobenzene mesogen, and the effects of the substituents were investigated. All the polymers were prepared at the ambient temperature by solution polycondensation with various 4‐substituted phenylazo‐4′‐phenyloxyhexylphosphorodichloridates and 4,4′‐bis(6‐hydroxyhexyloxy) azobenzene. The polymers were characterized with gel permeation chromatography, Fourier transform infrared, and ¹H, ¹³C, and ³¹P NMR spectroscopy. Thermogravimetric analysis revealed that all the polymers had high char yields. The liquid‐crystalline behavior of the polymers was examined with hot‐stage optical polarizing microscopy, and all the polymers showed liquid‐crystalline properties. The formation of a mesophase was confirmed by differential scanning calorimetry (DSC). The DSC data suggested that mesophase stability was better for electron‐withdrawing substituents than for halogens and unsubstituted ones. Ultraviolet irradiation studies indicated that the time taken for the completion of photoisomerization depended on the dipolar moment, size, and donor–acceptor characteristics of the terminal substituents. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3188–3196, 2003     

Observation of intercalated smectic phases in symmetric liquid crystal dimers containing hydrazide groups

Dimeric hydrazide derivatives with nitro, phenyl, and methyl terminal subsistents were synthesized. The liquid crystalline properties were investigated by differential scanning calorimetry, polarizing optical microscopy and wide angle X-ray diffraction. Interestingly, intercalated smectic phases were observed in these symmetric liquid crystal dimers. The effect of the substituents and the length of the spacer on the mesophase is discussed, confirming that intermolecular hydrogen bonding between the hydrazide groups was the driving force for the formation of the intercalated structures.     

X-ray diffraction study of the smectic mesophase of some azobenzene-containing polyacrylates

Abstract

An X-ray study is performed on powder specimens and on stretched oriented fibres of two liquid crystalline polyacrylates containing the azobenzene mesogenic unit with either a 4′-n-pentyloxy (sample 1–4) or 4′-n-hexyloxy (sample 1–5) substituent. The X-ray diffraction patterns of both samples showed the presence of a bilayer smectic C mesophase with the mesogneic groups tilted by an angle β ～ 45° (1–4) or β ～ 38° (1–5) with respect to the layer normal. The electron density profile p(z) along the direction normal to the smectic layers was calculated by Fourier inversion and possible structural models of the smectic mesophase are discussed. A partial interdigitation of the terminal alkyloxy substituents appears to occur.