Discotic liquid crystals derived from polycyclic aromatic cores: from the smallest benzene to the utmost graphene cores

ABSTRACT

Past decades we have witnessed many breakthroughs in research on liquid crystals (LCs) as well as significant amplification in the application of LCs. LCs are currently attracting great attention of scientists from all over the world where various researches have been implemented on the varied facets of LCs. In this review we present some recent developments in the field of discotic liquid crystals (DLCs). A large number of DLCs from various aromatic cores have been realised. However, due to paucity of space only DLCs derived from four main aromatic cores, benzene, triphenylene, hexabenzocoronene and graphene, are covered here. An outlook on these emerging two-dimensional organic semiconductor materials with relevant scientific application background has been presented.     

Nature of disclination cores in liquid crystals

A disclination is an orientation symmetry-breaking defect and its strength corresponds to the number of rotations (in multiples of 2π) of the director over a path encircling the disclination. The line core plays a considerable role in the disclination energy balance and mobility, however, the detailed nature of the core structure is largely unknown. Here we demonstrate different core structures for different disclinations by using transmission electron microscopy and atomic force microscopy coupled with the nanostripe decoration technique. We show that the molecular distribution in the core of (+1) defects changes from the prolate planar to oblate homeotropic, resembling but not identical to 'escape into the third dimension'. The homeotropic (-1) defect appears to possess an isotropic core, contrary to theoretical predictions.     

Dual frequency liquid crystals: a review

We review the recent progress in developing high performance dual frequency liquid crystal (DFLC) materials. A new figure of merit is derived for evaluating the DFLC performance. The dielectric relaxation and electro-optical properties of several high performance compounds, which possess a positive dielectric anisotropy at low frequencies and a relaxation frequency in the kilohertz region, are presented. Potential applications of these compounds are discussed. Compounds with a negative dielectric anisotropy were also compared and discussed. Two experimental DFLC mixtures were demonstrated with one intended for room temperature operation and another for elevated temperature operation.     

Triphenylene-based discotic liquid crystals: recent advances

Since the early work of Chandrasekhar and his co-workers on hexaesters of benzene published in 1977, discotic liquid crystals (DLCs), in particular, triphenylene-based DLC materials have been investigated intensively, especially over the last decade. The first successful commercialisation of triphenylene-based DLCs has been accomplished in Fuji ‘Wide-View’ optical compensation films. DLCs represent a broad well understood class of soft matter which possess the ability to self-organise into highly anisotropic and ordered structures such as columns that function not only as organic anisotropic semiconductors, but also contribute to the development of new smart materials in the field of organic electronics for many device applications such as photovoltaic devices, light-emitting diodes, field-effect transistors, memory elements, and sensors. Over the last 35 years, more than 1000 triphenylene derivatives have been synthesised and investigated starting from structure-properties to structure-device performance relationships. The very first review by Cammidge and Bushby followed by Kumar summarised the chemistry and physical properties of triphenylene-based discotics up to 2003. In this review, progress in the research of triphenylene DLC materials since 2004 is comprehensively outlined.     

Enaminoketones as calamitic liquid crystals with a novel hydrogen-bonded rigid core

A series of compounds having an aminopropenone-3 group between two aromatic rings has been synthesized and thermally stable enantiotropic mesogens with properties typical of three ring liquid crystals were obtained. The mesomorphic properties of the molecules result from the presence of a rigid calamitic core stabilized by a hydrogen-bonded cis-s-cis quasi-ring form of the enaminoketone group.     

Thermoplastic starch blends: A review of recent works

The aim of this review is to discuss the recent developments in thermoplastic starch blends. Starch has been considered as an excellent candidate to partially substitute synthetic polymer in packaging, agricultural mulch and other low-cost applications. Recently, the starch granules were plasticized using different plasticizers under heating and shearing, giving rise to a continues phase in the form of a viscous melt which can be processed using traditional plastic processing techniques, such as injection molding and extrusion. This kind of starch composites is called thermoplastic starch. Unfortunately, thermoplastic starch presents some drawbacks, such as low degradation temperatures, which make it difficult to process, poor mechanical properties and high water susceptibility. Much work has been carried out to overcome these drawbacks, including the combination of thermoplastic starch with other polymers, aiming at lowering the cost and enhancing the biodegradability of the final product.     

Synthesis of novel liquid crystal compounds with aromatic amide mesogenic cores

The synthesis and properties of a new series of compounds having aromatic amide mesogenic cores are reported. Most of these new compounds are thermotropic mesogens. In consideration of the fact that aromatic amides form crystals of high melting point which is unfavourable for the formation of thermotropic liquid crystals, we make use of lateral substitution to decrease both the packing efficiency and the hydrogen bonding, so that the melting temperature of the aromatic amides is sufficiently depressed. The lateral substituent used in these new compounds is bromine. In order to investigate the influence on properties of the end groups, different alkoxy, alkyl and other groups are used at the two ends of the rod-like molecules. The two ends are either identical or different, with an electron-donating alkoxy as one end and the electron-accepting cyano group as the other. The results indicate that appropriate lateral and terminal substitution is essential for the aromatic amides to form thermotropic liquid crystals. The peculiar mesophase characterized by an X-ray diffraction pattern of a SmC phase, but a texture of a nematic phase is also noted.     

Ferroelectric liquid crystals with fluoro- and aza-fluorenone cores: the effect of stereo-polar coupling

The chiral fluorenone mesogens (R)-1-fluoro-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)fluoren-9-one (2) and (R)-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)-3-azafluoren-9-one (3) were synthesized using a combined ortho-directed and remote metalation strategy, which also incorporates a Suzuki-Miyaura crosscoupling step. These compounds form chiral SmC* liquid crystal phases with reduced polarizations (P _o) of +475 and +332 nC cm^-2 at 10 K below the Curie point, respectively. These values are considerably larger than that previously reported for the unsubstituted fluorenone (R)-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)fluoren-9-one (1), which is +111 nC cm^-2 at 10 K below the Curie point. Molecular modelling based on the Boulder model suggests that the larger polarizations result from a conformational bias of the fluorenone core dipole moment along the polar axis of the SmC* phase caused by stereo-polar coupling with the chiral 2-octyloxy side chain.     

Polycatenar mesogens with a perfluorinated moiety showing a variety of liquid crystalline polymorphism

Polycatenar materials composed of a four-aromatic-ring core, with either a bulky or end-branched perfluorinated moiety attached at one end through a methylene spacer group, and three peripheral alkoxy chains of varying length (the carbon number n = 4, 6, 8, 10, 12, 14, 16) on the other end-ring, were synthesized to investigate the roles of the chemical structure of the compositional segments in relation to liquid crystalline phase formation. It was found that a homologous series of polycatenar materials exhibited a variety of liquid crystalline phases strongly dependent on the length of the peripheral alkyl chains. Moreover it was shown that changes in the spacer group and in the structure of the perfluorinated segment had a significant influence on mesophase formation.     

Cholesteric pitch of rigid and semi-flexible chiral liquid crystals

We calculate using mean field theory, the cholesteric pitch in systems composed of chiral molecules, which we model as 'corkscrews'. We consider both the rigid and semi-flexible limits. Our result for the cholesteric pitch depends on the intrinsic molecular pitch length as well as the concentration of molecules, but does not depend on the flexibility of the molecule.     

Ferroelectric liquid crystals with axially chiral 2,2′-spirobiindan-1,1′-dione cores

The axially chiral mesogens 5-alkoxy-5′-[(4-alkoxybenzoyl)oxy]-2,2′-spirobiindan-1,1′-dione (QL7-n) were synthesised as racemic mixtures and resolved as single enantiomers by preparative chiral phase HPLC. The shorter homologues (R)-QL7-8 and QL7-9 form enantiotropic N* and SmC* phases, whereas the longer homologues (R)-QL7-10 and QL7-12 form an enantiotropic SmC* phase only. Texture analysis showed that the helical pitch of the N* phase is below the wavelength range of visible light; a helical pitch of 187 nm was measured at T – T_NI = –5 K by selective reflection using enantiomerically enriched mixtures of (R)- and (S)-QL7-8 (0.35 ≤ ee ≤ 0.80). Spontaneous polarisations were measured as a function of temperature in the SmC* phase by the triangular wave method. P_S values at saturation range from 102 nC cm^–2 for (R)-QL7-8 to 120 nC cm^?2 for (R)-QL7-9, which are up to three times greater than the highest polarisation previously reported for an axially chiral SmC* mesogen. Optical tilt angles θ were measured as a function of temperature and showed a sharp rise consistent with first-order N*–SmC* or I–SmC* transitions, with values at saturation ranging from 42 to 44°.     

Thermotropic and lyotropic liquid crystalline phases of rigid aromatic amphiphiles

Rodlike amphiphilic molecules that contain exclusively aromatic building-blocks and no flexible alkyl chains have been synthesized and their mesomorphic properties investigated. These novel compounds bear diol head groups of different size (2,3-dihydroxypropyloxy or 5,6-dihydroxy-3-oxahexyloxy groups) at one end of a biphenyl unit, various aromatic segments (benzyloxy, 4-, 3-, or 2-methylbenzyloxy, phenoxy groups) at the other, and additional methyl substituents in different positions. They were synthesized by using Suzuki cross-coupling reactions as the key steps. Their thermotropic mesomorphism was investigated by means of polarized light optical microscopy, differential scanning calorimetry, and, for enantiotropic phases, by X-ray scattering. The liquid crystallinity of this class of compounds is influenced by protic solvents, such as water and glycerol. Dependent on the temperature and the solvent content, different SA phases were found. Several mesophases resulting from the frustration of these layer structures (e.g., different columnar phases, optical isotropic mesophases, and nematic phases) were also present. The smectic phases have different degrees of intercalation (SAd, SA2). The columnar phases are supposed to be ribbon structures that result from the collapse of the smectic layers. They occur in some pure compounds or they are induced upon the addition of protic solvents. The particular phase sequences of the different compounds depend mainly on the position of the methyl substituents at the biphenyl cores and are largely determined by the degree of intercalation of the aromatic cores.     

Ferroelectric liquid crystals induced by dopants with axially chiral 2,2'-spirobiindan-1,1'-dione cores

The axially chiral dopants (R)-5,5'-, 5,6'-, and 6,6'-diheptyloxy-2,2'-spirobiindan-1,1'-dione ((R)-2, -3, and -4) were synthesized in optically pure form, and their absolute configurations were assigned by the exciton chirality method using circular dichroism spectroscopy. These new compounds were doped in four achiral liquid crystal hosts to give chiral smectic C* (SmC*) phases with spontaneous polarizations (Ps) that vary with the core structure of the host. The spontaneous polarization induced by the 5,5'-dialkoxy derivative (R)-2 is uniformly positive, whereas that induced by the 6,6'-dialkoxy derivative (R)-4 is uniformly negative and shows a different trend in host dependence. Polarization power (delta(p)) values range from +21 nC/cm2 for (R)-2 in 2',3'-difluoro-4-heptyl-4' '-nonyl-p-terphenyl (DFT) to -1037 nC/cm2 for (R)-4 in 4-(4'-heptyl[1,1'-biphen]-4-yl)-1-hexylcyclohexanecarbonitrile (NCB76). The unsymmetrical dopant (R)-3 behaves like a hybrid of the two symmetrical isomers, with lower absolute values of delta(p), on average, and varying signs of Ps. 2H NMR spectra of the doped mixtures using racemic mixtures of 2-4 with -OCD2C6H13 side-chains, in combination with phase diagrams, show that relatively minor changes in the dopant structure, that is, moving the alkoxy side-chains from the 5,5' to the 6,6' positions of the spirobiindandione core, have profound effects on dopant-host compatibility, and on the propensity of the dopant to exert chiral perturbations in the host environment. The variations in sign and magnitude of delta(p) as a function of alkoxy group positions are rationalized based on an analysis of zigzag conformations that conform to the binding site of the SmC host according to the Boulder model.     

含有长烷氧链混合醚-酯类苯并菲盘状液晶的合成及其介晶性研究

本文合成了含有不同柔链的对称和非对称苯并菲盘状液晶:sym-C18H6(OC11H23)3(O2CR)3和asym-C18H6(OC11H23)3(O2CR)3,R=(CH2OC2H5),CH2OC3H7,CH2OC4H9,CH2OC5H11,C3H7,C4H9,C5H11,C6H13,C7H15。通过偏光显微镜(POM)和差视扫描量热法(DSC)对它们的热致液晶性性进行了研究,结果显示:非对称性化合物比它们相应的对称性化合物有更高的熔点和清亮点。对于同一系列的化合物G18H6(OC11H23)3(OOCR)3,随取代基R的增长,其熔点下降,清高点反而升高。无论对称和非对称苯并菲衍生物G18H6(OC11H23)3(O2CR)3,(R=CH2OC2H5,CH2OC3H7,CH2OC4H9,CH2OC5H11),与有同样软链长度的苯并菲衍生物G18H6(OC11H23)3(O2CR)3,(R=C4H9,CK5H11,C6H13,C7H15)相比较,大都有更高的熔点和清亮点。另外,有足够长度软链的苯并菲衍生物在室温下就显示介晶相。     

含有长烷氧链混合醚一酯类苯并菲盘状液晶的合成及其介晶性研究

本文合成了含有不同柔链的对称和非对称苯并菲盘状液晶：sym-C18H6（OC11H23），（02CR）3和nsym-C18H6（OCIIH23）3（02CR）3，R=（CH20C2H5），CH20C3H7，CH20C4H9，CH20C5H11,C3H7，C4H9，C5Hll,C6H13，C7H15。通过偏光显微镜（POM）和差视扫描量热法（DSC）对它们的热致液晶性性进行了研究，结果显示：非对称性化合物比它们相应的对称性化合物有更高的熔点和清亮点。对于同一系列的化合物G18H6（OC11H23），（OOCR）3随取代基R的增长，其熔点下降，清高点反而升高。无论对称和非对称苯并菲衍生物G18H6（OC18H23）3（02CR）3，（R=CH20C2H5，CH20C3H7，CH20C4H9，CH20C5H11），与有同样软链长度的苯并菲衍生物G18H5（OC11H23）3（O2CR）3，（R=C4H9，CK5H11,C6H13C，H15）相比较，大都有更高的熔点和清亮点。另外，有足够长度软链的苯并菲衍生物在室温下就显示介晶相。     

New chlorine-substituted ferroelectric liquid crystals with four aromatic rings in the mesogenic core

New series of liquid crystals with an alkyl-lactate chiral chain and four aromatic rings in the mesogenic core and chloro-substitution were synthesized. For all the compounds studied, SmA and SmC* phases, existing over very broad temperature ranges, were detected and characterized. Mesomorphic properties were analysed with respect to the lengths of the chiral and/or non-chiral chains.     

New chlorine-substituted ferroelectric liquid crystals with four aromatic rings in the mesogenic core

New series of liquid crystals with an alkyl-lactate chiral chain and four aromatic rings in the mesogenic core and chloro-substitution were synthesized. For all the compounds studied, SmA and SmC* phases, existing over very broad temperature ranges, were detected and characterized. Mesomorphic properties were analysed with respect to the lengths of the chiral and/or non-chiral chains.     

Determination of long range dipolar couplings in ferroelectric liquid crystals

Long range dipolar coupling constants have been determined in three ferroelectric liquid crystals in their racemic forms using ¹³C NMR. Two of these liquid crystals are esters of α-chloroacids and 4-octyloxy-4'-hydroxybiphenyl, and have a very large spontaneous polarization in the smectic C* phase. The strategy used in the present study is the observation and measurement of ²H-¹³C splittings in the ¹³C spectra of monodeuterated compounds. The order parameters were calculated from the 1D spectra, and some of the coupling constants are compared with the ¹H-¹³C coupling constants previously obtained from 2D experiments. In addition, the deuterium quadrupole splitting of these compounds was determined from their ²H NMR spectra. The experiments were carried out over the whole mesomorphic ranges of the liquid crystals, covering the smectic A and smectic C phases.     

Reminiscences from a life with liquid crystals

The author looks back over a scientific career of almost 50 years spent mainly in research on liquid crystals (LCs) and carried out largely in University service and latterly for about five years in Industry. In this review, the development through its rapid escalation starting in the early 1970s and stemming from the development of applications for LCs in electro-optical displays, itself set on course by the author's own discovery of the first materials enabling the production twisted nematic displays. The author's other contributions widened into a general review of current trends and activities in the field, with some emphasis being placed on threats to fundamental research posed by diminished funding and the current pressures on researchers to engage heavily in short term, 'wealth creating' projects. of UK LC research is traced mainly of commercially viable, long life in the field are discussed and