Synthesis and study of azo dye compounds: variation of mesogenic behaviour with length of alkyl chains

The mesogenic behaviours of two azo dye liquid crystals, 1 and 4, differ because of the different length of terminal alkyl chains; azo dye 1 shows a SmB phase, azo dye 4 shows nematic and SmA phases during thermal processing. The molecular stackings of these two azo dye liquid crystals are compared on the basis of crystallographic studies to explain such unexpected mesogenic behaviour.     

Azo compounds and Schiff 's bases derived from 5-(4-pyridyl)-2-amino-1,3,4-thiadiazole: synthesis, mesomorphic properties and structural study by semi-empirical calculations

The synthesis and liquid crystalline properties of new Schiff 's bases (series 3a-f) and azo compounds (4a-f) incorporating pyridine and 1,3,4-thiadiazole rings are reported. The first homologues in the series of Schiff's bases (3a-c) show a monotropic mesophase and the homologues 3d-f display an enantiotropic SmA phase. The only azo compounds to exhibit liquid crystalline properties are the homologues 4e, f which show a monotropic nematic phase. These series are compared with Schiff's bases and azo compounds analogues (series 5 and 6), previously reported by us and an AM1 study of the structure/mesomorphic property relationship is described.     

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

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.     

Monocyclic rod-type liquid crystals; 2,5-dialkanoyloxytropones and 5-alkanoyloxy-2-alkoxytropones

Two kinds of monocyclic troponoid mesogens, 2,5-dialkanoyloxytropones (4) and 5-alkanoyloxy2-alkoxytropones (5), were prepared. The former showed monotropic smectic A phases and the virtual isotropic liquid-smectic A transitions of the latter were determined by extrapolation of results in a binary phase diagram. Comparing the mesogenic properties between the tropones 4 and the 2-alkanoyloxy-5-alkoxytropones (1), the alkanoyloxy group at C-5 enhances both the melting points and the transition temperatures of the smectic A phases. From the comparison between 5 and 1 , the alkanoyloxy group at C-2 lowers the melting points.     

Synthesis and mesomorphic properties of a novel ladder-like 1,4-phenylene-bridged liquid crystalline polysiloxane containing ester-based mesogenic side groups

A new ladder-like 1,4-phenylene-bridged liquid crystalline polysiloxane bearing ester-based mesogenic side groups, LPLCPS, has been synthesized by hydrosilylation of a SiH-terminated ester-based mesogen compound (1) with a ladder-like 1,4-phenylene-bridged polyvinylsiloxane (LPPVS) containing vinyl-terminated side groups in the presence of dicyclopentadienylplatinum(II) chloride (Cp₂PtCl₂) catalyst. Compound 1 was synthesized by hydrosilylation of 1,1,3,3-tetramethyldisiloxane (HMM) with the vinyl-terminated ester-based mesogenic compounds. Various characterization methods including FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction were used and the results combined to demonstrate that LPLCPS shows thermotropic smectic mesomorphic behaviour with a high clearing point and a wide mesophase range.     

Pyrazolo[1, 2-a]pyrazoliumolates as novel structure elements in liquid crystals [1]

A series of pyrazolo[1, 2-a]pyrazoliumolates of type 3, 4, and 5 was prepared. Compound 4(R³ = CH₃) shows liquid crystalline properties (C 158.5 N 162 I).     

Thermotropic biaxial nematic phases with negative optical character [1]

Two disc-shaped multialkynyl arene ethers (1 and 2) with unusual thermo-mesomorphic properties are presented. Conoscopic studies show that the nematic phases of these new low molecular weight liquid crystals are biaxial and that the sign of their biaxiality is negative. The diether 2 is the first discotic twin liquid crystal which exhibits a nematic phase.     

Synthesis and characterization of new liquid crystalline materials containing a non-activated arylazoindolinobenzospiropyranyl group as a chiral unit. Part II

Two series of new liquid crystalline compounds containing a non-activated arylazoindolinobenzospiropyran, ABP-SPAB 1a-1e (series 1) and SPAP-ABPC 2a-2e (series 2), have been synthesized. These LC dyes were characterized by a differential scanning calorimetry polarizing optical microscopy, X-ray diffraction and electro-optical measurements. All but one of the series 1 compounds examined exhibit monotropic second and/or third transition liquid crystal phases on cooling from the isotropic liquid. In particular, ABP-SPAB 1b shows a monotropic SmC phase, in addition to a SmA phase. In series 2, most of the compounds exhibit a monotropic nematic phase on cooling. SPAP-ABPC 2c forms an enantiotropic nematic phase and a monotropic SmA phase; 2e shows enantiotropic nematic and SmA phases.     

Heterocyclic benzoxazole-based liquid crystals

The synthesis, characterization, and mesomorphic properties of a new type of heteronuclear compounds 1a-c and a Pd complex 1d derived from benzoxazole as the core group are reported. These compounds were prepared by the ring closure reaction of 4-alkoxybenzoic acid 4-[(4-alkoxy-2-hydroxyphenylimino)methyl]phenyl esters 6 in the presence of lead(IV) acetate. All the compounds were characterized by ¹H and ¹³C NMR spectroscopies and elemental analysis. The phase behaviour of these mesogenic compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All the compounds 1a exhibited nematic (N) and/or smectic C (SmC) phases, as expected for rod-like molecules; however, the compounds 1b and 1c exhibited crystal phases. For those compounds 1a having shorter carbon chains (n = 1, 3, 4) nematic phases were observed, whereas for compounds having longer carbon chains (n = 6, 7, 8, 10, 12, 14) smectic C behaviour was also observed at lower temperatures. The greater aspect ratio (l/d) of compounds 1a compared with 1b and 1c was found to be required for the observation of liquid crystallinity. The fluorescent properties of these compounds were also examined. All λ_max peaks of the absorption and photoluminescence spectra of compounds 1a-1c occurred at c. 316-322 nm and 371-382 nm, respectively. The quantum yields of some compounds were relatively low, and also slightly solvent-dependent.     

Mesogenic behaviour of (4-alkoxybenzylideneamino)bromobenzene, (4-alkoxybenzylideneamino)benzenethiols, and thiolatonickel complexes of the thiols

The synthesis, characterization and mesogenic properties of Schiff base compounds arising from the reaction of 4-alkoxybenzaldehydes with 4-aminothiophenol or 4-bromoaniline are described. Whereas the Schiff base thiol with two benzene rings in the molecule, HSC₆H₄NC(H)C₆H₄OC₁₆H₃₃ (2), is non-mesogenic, the bromo analogue, BrC₆H₄NC(H)C₆H₄OC₁₆H₃₃ (3), is mesogenic. The introduction of a third benzene ring into the molecular architecture of 2 and 3 produced thiol- and bromo-Schiff base compounds, HSC₆H₄NC(H)C₆H₄OC(O)C₆H₄OC₁₆H₃₃ and BrC₆H₄NC(H)C₆H₄OC(O)C₆H₄OC₁₆H₃₃, respectively, that are both mesogenic. The thiol compounds react with nickelocene to form [(η ⁵-C₅H₅)Ni(μ ₂-SC₆H₄NC(H)C₆H₄OC₁₆H₃₃)]₂ and [(η ⁵-C₅H₅)Ni(μ ₂-SC₆H₄NC(H)C₆H₄OC(O)-C₆H₄OC₁₆H₃₃)]₂, but the nickel complexes are not mesogenic.     

Supramolecular Assemblies of Three New Metronidazole Derivatives Constructed with Various Dihydroxy-benzoic Acids via Hydrogen Bonds

Metronidazole(MTZ) is an important antibiotic, which has been widely applied to cure protozoal and bacterial diseases for human beings or animals. Herein, three novel drug supramolecular crystals constructed by MTZ with 2,5-dihydroxy-benzoic acid(2,5-DHBA)(1), 2,6-dihydroxy-benzoic acid(2,6-DHBA)(2) and 3,5-dihydroxy-benzoic acid(3,5-DHBA)(3), respectively, have been discovered. The hydrogen bonds of N-H···O(O-H···N), C-H···O and O-H···O play important roles in the 3D supramolecular framework formation for crystals 1-3. Interestingly, due to the vary locations of the substituent groups, the two-dimensional layers in crystals 1 or 2 are constructed via intermolecular hydrogen bonds between MTZ and 2,5-DHBA or 2,6-DHBA, while in crystal 3 water molecules play a significant role except the intermolecular hydrogen bonds between MTZ and 3,5-DHBA. In addition, five synthons of I R₂²(8), II R₃³(9) in crystal 1, III R₁²(4), IV R₂²(8) in crystal 2 and V R₂²(7) in crystal 3 formed through various hydrogen bonds are founded in this work. Systematic studies of syntheses, crystal structures and thermal analysis are reported.     

Liquid crystalline hexa-amides and side chain polysiloxanes of azacrown [18]-N6

The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N₆ was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N₆ has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH₂)₁₁ spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N₆ mesogen. The polysiloxanes also display a liquid crystalline phase.     

Synthesis and characterisation of main-chain hydrogen-bonded supramolecular liquid crystalline complexes formed by azo-containing compounds

A series of azopyridine-containing hydrogen bonding acceptors (4a-c) with flexible spacers of oligo(methylene) were synthesised. Hydrogen-bonded polymeric complexes 4/5 and trimeric complexes 4/6₂ , where 5 and 6 are aromatic dicarboxylic acids and monocarboxylic acids, respectively, were prepared and their liquid crystallinity was examined using differential scanning calorimetry and polarising optical microscopy. The study showed that most of the complexes displayed reversible thermotropic nematic phase. The isotropic to nematic phase transition temperatures of polymeric complexes 4/5 and trimeric complexes 4/6₂ in general decreased with the increase in length of spacers and terminal groups in the corresponding proton acceptors 4 and the proton donors 5 and 6, respectively. Hydrogen bonding interactions in complexes 4/5 and 4/6₂ were studied by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy.     

In plane and out of plane anisotropy in Langmuir-Blodgett films of discogenic molecules

Langmuir-Blodgett films of a discotic mesogenic pyrylium tetrafluoroborate salt (1) have been investigated from the point of view of their in-plane anisotropy, i.e. considering the average molecular orientation with respect to the dipping direction. The molecules are found to stand on edge with their flat polycyclic core more or less perpendicular to the dipping direction. Mixing 1 with N(C₄H₉)₄⁺ TCNQ^- in the spreading solvent leads to a different behaviour of the monolayer at the air-water interface, involving the formation of the Pyrylium-TCNQ salt. In contrast to the films of pure 1, these films do not exhibit any in-plane anisotropy after deposition on a solid substrate. The temperature dependance of the molecular anisotropy of both films has also been investigated. The results are presented and discussed in the framework of their mesomorphic properties together with the influence of the anion associated with Pyrylium.     

A new series of nematic and smectic liquid crystals with negative dielectric anisotropy: the effect of terminal chain substitution on thermal and electro-optical properties

Two alkyl (1b and 1c) and four fluoroalkyl derivatives (1d-1f) of 4-arylbutyric acid (1c, 1d and 1e) and 4-arylbutanol (1b, 1f and 1g) [aryl = 2',3'-difluoro-4'-(2-(E-4-pentylcyclohexyl)ethyl)-biphenyl-1-yl] were prepared and investigated in the pure form as nematic materials (1b and 1c) and as additives to a ferroelectric liquid crystal (FLC) host (1d-1f). A comparison of 1b and 1c with the decyl analogue 1a demonstrates the effect of terminal chain modification on thermal and electro-optical properties. The substitution of the -CH₂O- (1b) or -COO- (1c) for -CH₂CH₂- in 1a destabilized the N and SmA phases or completely eliminated the smectic behaviour (1c). Dielectric analysis revealed that the chain modification increased the negative Δε, reduced elastic constant K ₁₁ and moderately decreased rotational viscosity γ₁. The temperature dependence of the key electro-optical parameters was analysed for ester 2, the methyl analogue of 1c, which exhibits a 45 K wide N phase. All four fluoroalkyl derivatives 1d-1f showed enantiotropic SmA phases and 1e also exhibited a monotropic SmC phase. Solutions of 1d-1f in a FLC host (0.2 mmol g^-1) increased the tilt angle Θ (up to 45° for 1g), reduced rotational viscosity γ₁ and the risetime τ. The most dramatic changes were observed for 1g, which contains 15 fluorine atoms.     

CPI induction of liquid crystal behaviour in triphenylenes with a mixture of hydrophobic and hydrophilic side chains

2,3,6,7,10,11-Hexasubstituted triphenylenes have been synthesized that contain a mixture of hydrophobic (C₆H₁₃O) and hydrophilic (CH₃OCH₂CH₂OCH₂CH₂O) side chains. At one extreme HAT6 (1a) (six hydrophobic chains) shows thermotropic behaviour and at the other TP6EO2M (1e) (six hydrophilic chains) shows lyotropic behaviour. Of the triphenylenes with a mixture of hydrophobic and hydrophilic side chains, only the triphenylene with one hydrophilic side chain and five hydrophobic side chains (1b) gives a thermotropic columnar phase. None of the others show liquid crystal behaviour. However, all of these triphenylenes form binary 1:1 compounds when mixed with PDQ9 (2a) and with PTP9 (2b). These CPI (complimentary polytopic interaction) stabilized compounds give thermotropic hexagonal columnar phases over wide temperature ranges.     

Crystal structures of ferro- and antiferroelectric mesogens with a 1-methylalkoxycarbonyl group

Crystal structures have been determined for 4-[(S)-1-methylpentyloxycarbonyl]phenyl, 4-([S)-1-methylhexyloxycarbonyl]phenyl 4'-octyloxybiphenyl-4-carboxylates (1 and 2, respectively) and (R)-1-methylheptyl 4-(4'-octyloxybiphenyl-4-yloxymethylene)benzoate (3), which have S_CA*, S_C* and S_CA* phases, respectively. All the crystals have a common packing mode with the previously determined structure of 4-(1-methylheptyloxycarbonyl)phenyl 4'-octyloxybiphenyl-4-carboxylate (MHPOBC). Each crystal forms a smectic-like layer structure composed of largely bent molecules with the long alkyl chain of the chiral group almost perpendicular to the core moiety. Differential scanning calorimetry showed that the crystals of 1, 2, and MHPOBC, which have a carbonyloxy group as the central linkage between the biphenyl and phenylene moieties, transform to higher temperature solid phases in a similar temperature range (around 60°C). For 3, which has an oxymethylene linkage between the biphenyl and phenylene moieties, three kinds of solids were distinguished.     

New smectic C mesogens containing the benzyl, phenylethyl or phenylpropyl moiety

A series of compoumds, benzyl 4-(4'-alkyloxybiphenyl-4-carbonyloxy)benzoates (1-10), and the two analogous compounds phenylethyl 4-(4'-octoxybiphenyl-4-carbonyloxy)benzoate (11) and phenylpropyl 4-(4'-octoxybiphenyl-4-carbonyloxy)benzoate (12), were prepared. The compounds 6-12 exhibit a SmC phase in addition to other smectic phases. Compound 11, exhibits a nematic phase.     

Synthesis and properties of optically active 1,3-diols and their derivatives as chiral dopants for ferroelectric liquid crystals

New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1.     

New 1,2,4- and 1,3,4-oxadiazole materials: synthesis, and mesomorphic and luminescence properties

The synthesis and liquid crystalline properties of new series of 1,2,4- and 1,3,4-oxadiazole derivatives (2a-f and 5a-f respectively) are reported. These compounds contain only one terminal flexible alkoxy chain, the other terminal substituent is a protecting benzyl group. All compounds of series 2 exhibit an enantiotropic nematic phase. The homologue with the longest chain (2f) displays an enantiotropic dimorphism smectic A- nematic. None of the compounds of series 5 shows mesomorphism and only crystal-isotropic transitions were observed. The liquid crystalline properties were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray measurements. Luminescence properties, in chloroform solution, of 2f and the series 5 compounds were evaluated. Good photoluminescence quantum yields for compounds of series 5 were observed. Compound 2f, incorporating the 1,2,4-oxadiazole ring shows a very strong reduction in emissive properties.