Mesophase Stability Research Articles

Supramolecular liquid crystals displaying competitive hydrogen bonding: Small molecule mesogens assembled through different hydrogen bond assemblies

ABSTRACTA series of supramolecular assemblies created through competitive hydrogen bonding of a n-alkoxy benzoic acid hydrogen bond donor and a mixture of hydrogen bond acceptors: a liquid crystal-forming rigid bi-pyridyl and a non-mesogenic tetrafunctional pyridyl species. The associative chain structures displayed mesogenic characteristics at loadings dependent on the concentration of the disruptive tetrafunctional agent- systems eliminated liquid crystallinity at 85% inclusion in heating transitions and 90% in cooling. The assembled structures displayed considerable mesophase stability. This was observed through long liquid crystalline lifetimes even at high compositions of 4PD, which generally dampened due to a generalized eutectic effect. It is believed that the freedom of mobility inherent in the C8 Acid allows for the reorganization of the hydrogen bonds in the liquid crystalline state providing for a very high loading of disruptor and long mesophase lifetimes.

Thermotropic liquid crystalline polyesters derived from 2-chloro hydroquinone

Synthesis of thermotropic liquid crystalline polyesters derived from bis[4-hydroxy benzoyloxy]-2-chloro-1,4-benzene (BHBOCB) and aliphatic dicarboxylic acid chlorides by interfacial polycondensation methodology is presented. Synthesised polyesters consist of bis[4-hydroxy benzoyloxy]-2-chloro-1,4-benzene as a mesogen and aliphatic diacid chloride as flexible spacer. The length of oligomethylene units in the polymer was varied from the trimethylene to the dodecamethylene groups. Synthesized polyesters were characterized by differential scanning calorimetry and optical microscopy. The transition temperatures and thermodynamic properties were studied for all these polymers. These polyesters exhibited thermotropic liquid crystalline behavior and showed nematic texture except decamethylene spacer. Decamethylene spacer based polyester showed marble texture of smectic C. Mesophase stability of these polyesters was higher than $$123{^{\circ }}\hbox {C}$$ (except first heating cycle of PE-1). SYNOPSIS The present study deals with the synthesis of thermotropic liquid crystalline polyesters derived from bis[4-hydroxy benzoyloxy]-2-chloro-1,4-benzene (BHBOCB) and aliphatic dicarboxylic acid chlorides by interfacial polycondensation methodology.

Probing the structural features that influence the mesomorphic properties of substituted dibenz[a,c]anthracenes

We report the synthesis and mesophase characterization of a series of novel hexaalkoxydibenzanthracenes to probe the effect of side-chain length variation and substituents on the mesophase temperature range. A series of hexaalkoxydibenz[a,c]anthracenes (2a–2i) with varying chain lengths were prepared by Suzuki coupling of the appropriate boronate ester with the corresponding dialkoxydibromonaphthalenes, followed by oxidative cyclization. Compounds 2a–2i were also brominated in the 10 and 13 positions to yield the corresponding dibromo series, 4a–4i. While none of the compounds, 2a–2i, exhibited columnar mesophases, all of the compounds in series 4a–4i did exhibit columnar phases over broad temperature ranges. To further investigate the effect of substituents on the mesomorphic properties of hexaalkoxydibenzanthracenes, we also prepared iodo-substituted 8, nitro-substituted 9, and amino-substituted 10. A comparison of the mesophase temperature range with previously reported compounds 3–7 shows that electron-withdrawing groups promote the formation of stable mesophases. However, our results also suggest that the substituents affect mesophase stability by participating in intermolecular contacts within the columnar stacks of the mesophase.

Preparation and characterisation of laterally monofluorinated mesogenic benzimidazole-based compounds

ABSTRACTSeries of laterally monofluorinated compounds, 2-(4ʹ-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.

Preparation and properties of laterally multifluorinated benzoxazole-based nematic mesogens

ABSTRACTSeries of laterally multifluorinated heterocyclic compounds, 2-(2ʹ,3-difluoro-4ʹ-alkoxy-1,1ʹ-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.

Composite liquid crystal-polymer electrolytes in dye-sensitised solar cells: effects of mesophase alkyl chain length

ABSTRACTThe doping of polymer electrolytes (PEs) with liquid crystal (LC) materials has been shown to improve the performance of dye-sensitised solar cells (DSSCs). This is achieved by promoting ionic conduction and increasing optical path length through multiple-light scattering within the photovoltaic devices. In LCs, it is well known that the length of the alkyl chain plays an important role since the LC morphology and mesophase stabilisation depend strongly on the alkyl group. In this work, liquid crystal-polymer composite electrolytes (LC-PEs) are prepared using nematic LCs with different alkyl chain lengths. The morphology of the LC-PEs is investigated and correlated with their electrical properties. Subsequently, DSSCs are prepared using the LC-PEs as a direct example of its application. It is shown that increasing the alkyl chain length of the LCs reduces the efficiency of the solar devices. The longer alkyl chains are speculated to intertwine, thus trapping the mobile ions and reducing the bulk ionic conductivity. For the same reason, longer alkyl chain LCs are thought to be unable to passivate the TiO2 surface through the adsorption of cyanobiphenyl groups and hence the higher probability of back recombination reaction between the electrons in TiO2 and PE.

Crowded Star Mesogens: Guest-Controlled Stability of Mesophases from Unconventional Liquid-Crystal Molecules.

The molecular design of crowded hexasubstituted star mesogens based on a benzene core and alternating substitution with oligo(phenylenevinylene) arms and aryl units generates free space between the conjugated arm scaffolds. Various arylcarboxy building blocks, decorated with alkoxy chains, have been incorporated in the void by mixing, hydrogen bonding or covalent bonds to the aryl groups. The mesogens assemble in columnar stacks ranging from soft crystals to rectangular and hexagonal columnar liquid crystals, revealed by polarized optical microscopy, differential scanning calorimetry, X-ray scattering and modelling. The stability of the mesophases is crucially influenced by the binding mode of the arylcarboxy guest building blocks. The origin of the variation in clearing temperature is unravelled by modelling, cohesive energy density considerations and solid-state NMR spectroscopy. The control over the transition temperature is important for the formation of aligned thin films and thus for potential applications.

Synthesis, Mesomorphism and Photoluminescence of a New Class of Anthracene-based Discotic Liquid Crystals

Four discotic liquid crystals (DLCs) based on anthracene, a novel redox active central core, have been synthesized and their mesomorphic behavior investigated. Among them, two of the derivatives showed stable hexagonal plastic mesophases whereas other two exhibited a columnar nematic phase at near room temperature as derived by X-ray scattering results. Type of the mesophases formed by these new class of compounds are rare that renders the central anthracene core attractive in the search for new functional DLC materials. HOMO-LUMO values have also been found to be much less in these materials which make them as good candidates for electron migration studies in self-organized systems. All the compounds show blue luminescence in solution under the long wavelength UV light. Overall, these new class of materials are promising, considering the emissive nature, ease of synthesis and stabilization of unconventional mesophases at room temperature or near room temperature.

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

ABSTRACTA 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 (λmax) of nearly 370 nm.

The effect of orientation of the lateral methyl substituent on the mesophase behaviour of 4-alkoxyphenylazo aryl benzoates

ABSTRACTTwo homologous series of 4-alkoxyphenylazo 4ʹ-(2ʺ- (and 3ʺ-) methyl-) 4ʹ-substituted benzoates (IIna–f and IIIna–f, six series each) were prepared and investigated. Within each series, the length of the terminal alkoxy group varies among 6, 8, 10 and 12 carbons, while the other terminal substituent, X, is a polar group that alternatively changes between the electron-donating CH3O, CH3, and the electron-withdrawing Br, NO2 and CN groups, in addition to the un-substituted analogue, X = H, aiming to investigate the effect of the different orientations of the methyl groups substituted on the central benzene ring, on the mesophase behaviour. The mesomorphic properties were discussed in terms of steric and polarisability effects. The mesophase stability was correlated with the polarisability anisotropy of bonds to the terminal substituent X. Comparative studies were made between the prepared isomers with each other and with the previously investigated laterally neat analogues 4-(4ʹ-alkoxyphenylazo) phenyl 4ʺ-substituted benzoates (Ina–f).

Main-chain liquid crystalline copolymers: synthesis and comparative study of the mesomorphic properties and non-linear optical properties

ABSTRACTLinear main-chain polymers (P1, P2 and P3) have been synthesised and characterised. The polymers were designed to understand the rigidity of the mesogen’s linking groups and its effect on transition temperature. The liquid crystalline behaviour of these polymers was investigated using polarised optical microscopy and differential scanning calorimetry. All polymers exhibited phase transition on heating and cooling runs. The mesophase stability decreases with the decrease of rigidity of the second mesogen (P2>P1>P3). Similarly, the enthalpy and entropy changes are dependent on the rigidity of the second mesogen (Mesogen B). Polymer P1 undergoes photoisomerisation under UV-visible light irradiation and it attains a photo-stationary state at 275 s. This provides an opportunity to investigate the third-order non-linear optical properties. The non-linear behaviour of polymer P1 in chloroform presents a distinct deviation in a different concentration, where polymer P1 also exhibits a negative non-linear refractive index. Thus, polymer P1 can be used as a potential candidate for optical device applications such as optical limiters.

Playing with nanosegregation in discotic crown ethers: from molecular design to OFETs, nanofibers and luminescent materials

ABSTRACTDiscotic liquid crystals are promising materials for electronic device applications. Combining extended π-systems with crown ethers may further open access to functional supramolecular hybrid materials. In the present publication, we briefly summarise recent literature developments and focus in a second part on our work in the field of discotic crown ethers. The crown ether derivatives are conveniently accessible by convergent syntheses which allow a high degree of variation with respect to side chains, mesogenic unit, size and symmetry of the crown core, metal complexation and counterion. This set of compounds provides a basis for systematic structure–property relationship investigations. Numerous experimental studies identified factors being crucial for mesophase stabilisation and geometry and furthermore led to novel room-temperature crown ether mesogens. The latter were obtained by congestion of the mesogenic units and even introduction of peripheral δ-methyl branched side chains. The formation of molybdenum clustomesogens and their application as luminescent hybrid materials is also described.

Smectic A mesophases from luminescent sandic platinum(II) mesogens

ABSTRACTSquare planar platinum(II) thienyl pyridyl complexes with board-shaped structures assemble into lamellar (SmA) liquid crystal phases at elevated temperatures. Liquid crystals of this type are expected to have stronger biaxial correlations than typical calamitic mesogens. The mesophase stability improves with decreasing alkyl chain lengths with C8H17 having the widest range of stability. All complexes are luminescent in solution.

Photoluminescent discotic liquid crystals derived from tris(N-salicylideneaniline) and stilbene conjugates: Structure–property correlations

Luminescent discotic liquid crystals based on tris(N-salicylideneaniline)s [TSANs] bearing trans-stilbene fluorophores have been synthesized. Their mesomorphic and photophysical properties were studied. These TSANs existing in the form of C3h and Cs geometrical isomers of the keto-enamine tautomer self-assemble to form the columnar phase and exhibit fluorescence both in solution and mesophase states. These columnar mesophases also exhibit frozen (glassy) columnar phase, which ensures preserved fluorescence intensity, defect free alignment and simultaneous restriction on the motion of ionic impurities. These features make them promising candidates for the use in organic light emitting diodes, particularly as emissive layers. This study also led to an understanding about the dependence of their mesomorphism (mesophase type, stability and thermal range) and photophysical features on the number and pattern of their peripheral substitution, in comparison to the analogous columnar liquid crystalline TSANs reported earlier.

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

ABSTRACTA series of nematic heterocyclic liquid crystals, 2-(2ʹ-fluoro-4ʹ-alkoxy-1,1ʹ-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.

PDLC composites based on polyvinyl boric acid matrix – a promising pathway towards biomedical engineering

ABSTRACTPolymer dispersed liquid crystal (PDLC) systems based on a smectic liquid crystal embedded in polyvinylalcohol-boric acid (PVAB) as biocompatible carrying matrix were prepared and characterised. The smectic liquid crystal contains biologically friendly structural blocks and was designed to have a direct isotropic–smectic transition and a mesophase stability range at human body temperature. The resulted PDLCs were characterised from morphological and thermotropic aspects by polarised light microscopy (POM), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and Raman microspectroscopy, and their surface properties were determined by contact angle measurements and surface energy calculations.It was concluded that the electron-deficient PVAB matrix constrains the ester liquid crystal to grow as spherical droplets with planar anchoring. The droplet diameter was comprised in the range 4–11 µm, with a predominant droplet population around 7 µm and a narrower polydispersity as the amount of the liquid crystal in the polymeric matrix increases. The resulted PDLC films exhibited versatile morphology and surface properties which allow targeting of their application.

Ionic liquid crystals based on viologen dimers: tuning the mesomorphism by varying the conformational freedom of the ionic layer

ABSTRACTWe investigated the liquid crystal behaviour of newly synthesised bistriflimide salts of symmetric viologen dimers. A smectic A phase was observed for intermediate spacer lengths and for relatively long lateral alkyl chains. The systems were characterised by thermal analysis, polarised optical microscopy, X-ray scattering and solid-state NMR. An intermediate ordered smectic phase was also exhibited by the compounds (except for systems with very short lateral chains) consisting of molten layers of alkyl chains and partially ordered ionic layers. These results, relating to the mesomorphic behaviour of viologen salts, are qualitatively compared to those of the more common imidazolium salts, highlighting the importance of the conformational degrees of freedom of the anions and of the cationic core. It appears that fine tuning of the conformational degrees of freedom of the ionic layer is an important component of mesophase stabilisation.

Mesomorphic and fluorescence properties of methyl 4-(4-alkoxystyryl)benzoates

ABSTRACTA series of methyl 4-(4-alkoxystyryl)benzoates was synthesised and studied for liquid crystalline and fluorescence properties. The peculiarity of the reaction scheme involved condensation between 4-alkoxybenzaldehyde and 4-(methoxycarbonyl)benzyltriphenyl phosphonium bromide in dichloromethane without any phase separation. The compounds were found thermally stable up to 200°C. The banded or arced focal-conic fan texture of CrE phase was exhibited on cooling the compounds (with chain length > C4) below the SmA phase. It was observed that increasing chain length up to C10 enhances mesophase stability. No LC behaviour was manifested by small (up to C3) and branched small chain (up to C4) members of the series.

Studies on Anisotropic Molecular Orientation and Mesophase Stability in a Ternary Mixture of Liquid Crystalline Materials

ABSTRACTThe multicomponent system of cholesteryl linolenate (CL), sodium oleate (Naol), and orthophosphoric acid (H3PO4) exhibits liquid crystalline mesophases, like cholesteric and smectic phases, such as SmA, SmC, SmB, and SmG sequentially when the specimen is cooled from its isotropic phase. These phases have been observed by using microscopic technique. Helfrich potential and elastic moduli have also been estimated in the smectic phase using Helfrich model. Optical transmittance and electrical conductivity have also been discussed.

Phase Transition and Optical Characterization of Mesophase Stability of Nematic and Columnar Biphasic Regions

We report the results of our studies on the optical and thermal properties of binary mixture of two compounds viz., abietic acid and alizarin dye. The mixture shows a very interesting co-existent biphasic regions of nematic (N + I) and columnar smectic (C + I) phases, sequentially when the specimen is cooled from its isotropic phase respectively at different concentrations of given molecule. The temperature variations of optical anisotropy, optical textures and electrical conductivity have also been discussed. Aggregated molecular size has been confirmed by X-ray studies.