Circularly polarized emission from a narrow bandwidth dye doped into a chiral nematic liquid crystal

We report on circularly polarized light emitted from a chiral nematic liquid crystal doped with a luminescent organolanthanide dye. The organolanthanide emission displays an extremely narrow spectral bandwidth of Δ λ_E≈ 8 nm. This is considerably narrower than the CNLC selective reflection bandwidth Δ λ_R≈60 nm. When conventional dyes with broader emission bandwidths are dissolved into CNLCs, the average degree of circular polarization g of emitted light is reduced from the maximum degree g _MAX ; this is due to the overlap of the emission band with the reflection band edges, and spectral regions outside the reflection band. Here, however, we can place the entire emission band inside the reflection band and achieve g ≈ g _MAX=1.27. Furthermore, a high degree of circular polarization is maintained under off-axis viewing up to a viewing angle of ≈ 30° to the normal.     

Mass transport in a chiral nematic/nematic liquid crystal system

The optical microscopic mass transport technique has been used to study diffusion phenomenon in a chiral nematic/nematic solute/solvent mixture. Analysis of the concentration-distance, concentration-time and distance-time of the diffusion profile gave the diffusion coefficient of the system as a function of time, distance and concentration, respectively. The mutual diffusion coefficient of the system was independent of the distance and time, showing an average value of 2.65 × 10^-7 cm² s^-1. In non-steady state diffusion, the diffusion coefficient was dependent on both distance and time. The diffusion coefficient exhibited an inverse relation with the local concentration of the chiral solute. The self-diffusion coefficient of the nematic solvent gave a value of 3.4 × 10^-7 cm² s^-1 via extrapolation to zero concentration of the solute.     

Circularly polarized luminescence based on cholesterol-tetraphenylethylene-perylene liquid crystal

Perylene derivative with circularly polarized luminescence（CPL） at aggregated state was seldom reported due to the strong ACQ（aggregation-caused quench） effect at aggregation. In this work, a novel cholesterol-tetraphenylethylene-perylene derivative（TPE-P） was designed and synthesized in moderate yield. It exhibited liquid crystalline behavior with orderly hexagonal columnar mesophase and good fluorescence emission at long wavelength（600-700 nm） not only in solution but also at aggregated states...     

Photoinduced liquid crystal blue phase by bent-shaped cis isomer of the azobenzene doped in chiral nematic liquid crystal

A photoresponsive azobenzene molecule DCAZO2 with two cholesteryl groups linked to both sides of the azobenzene group is doped in a mixture of nematic liquid crystal E7 and chiral dopant S811 (61.9 wt% E7, 36.1 wt% S811 and 2.0 wt% DCAZO2). Cooled from isotropic phase to 33.0°C, chiral nematic liquid crystal (N*LC) was formed in the sample and then the temperature was kept unchanged at 33.0°C. UV light irradiation induces the trans–cis photoisomerisation and thus an obvious phase transition. When the azobenzene groups isomerise to a cis-saturated state, the UV light was turned off and the white light was turned on at the same time. The bent-shaped cis isomer then turns back to the planar trans isomer gradually. A blue–green platelet texture representing cubic blue phase (BP) was observed and the size of the platelets was increased along with the cis–trans isomerisation. UV–vis absorption spectra indicate that the photoinduced BP exists when the isomerisation degree is between 79% and 18%, and further cis–trans isomerisation change BP back into N*LC. The large geometric structure of the cholesteryl groups and the large bent angle θ of the cis isomer are supposed to be responsible for the interesting result.     

Investigations of dual-frequency nematic liquid crystals doped with dichroic dye

In this work, we studied and analysed a particular variety of liquid crystals, the so-called dual-frequency nematic liquid crystals (DFNLCs). The interest was to perform dielectric spectroscopy and optical characterisation with two pure and doped mixtures of DFNLCs. By means the dielectric spectroscopy we observed a low value of crossover frequency at room temperature for one dye doped mixture. Additionally, in the spectra studies, a scattering of light at cross-frequency, and a stable and unstable focal conical state was observed, respectively, for the investigated mixtures.     

Light-induced Freedericksz transition in a nematic liquid crystal with chiral dopant

The influence of phototransformed molecules with chiralproperties changing on the absorption of light field on the light-induced Freedericksz transition threshold in a homeotropically oriented nematic cell is considered. It is shown that the appearance of the light-induced chiral molecules can decrease or increase the Freedericksz threshold value depending on the chirality sign of the phototransformed molecules and of the initial chiral dopant. Expressions for the threshold are obtained for circular and linear polarization of the incident light. The dependence of the threshold on the periodicity of the spatially modulated light intensity is estimated for large periods of modulation. The dependence of dopant threshold chirality on the director anchoring energy has been found.     

Morphological study of a chiral polymer network in a nematic liquid crystal from a concentration gradient

A contact preparation is made between a cholesteric photocrosslinkable material and a standard nematic liquid crystal. The concentration and the anisotropy progressively and homogeneously vary along a direction perpendicular to the diffusion front. On the basis of scanning electron microscopy investigations, comparisons are made between the modifications of the polymer network from a sample region rich in one component to the complementary region rich in the other. Such a preparation offers the opportunity to visualize the morphological transformations when a phase transition occurs and the morphologies intrinsic to textures intermediate between well-classified mesomorphic textures. Scanning electron microscopy texture observations are made in parallel with those by optical microscopy in order to make the connection with the mesomorphic textures, which therefore act as indicators during the subsequent SEM investigations.     

Modelling a nematic liquid crystal

The bulk phase liquid crystalline behaviour of a cyclic siloxane with a pentamethylcyclosiloxane core and biphenyl-4-allyloxybenzoate mesogens (BCS) was studied using molecular dynamics (MD) and wide angle X-ray analysis. This material exhibits partial crystallinity at room temperature and liquid crystalline behaviour above 120° C. For the MD simulations an ensemble of 27 molecules with 135 mesogenic units was simulated and a molecular mechanics force field was used to model the structural anisotropy of the siloxane molecules. Simulations were carried out both at room temperature and at an elevated temperature (425 K). Room temperature simulations showed that, contrary to our initial assumptions, the low energy molecular conformations were not cylindrical but splayed in shape. During the simulation a smectic-like, tilted layer structure was found to evolve for the cluster when full atom potentials were used, while no such development was observed when electrostatic interactions were neglected. The presence of a tilted layered structure was also suggested by the X-ray data. These results indicate that long range electrostatic interactions are significant for the molecular system under study. In order to calculate the orientational order parameter, the orientation of the molecular axis had to be determined. This was achieved by describing the mesogen shapes to be ellipsoidal and defining the principal axis of the ellipsoids to be the molecular directors. By sampling over 200 ps of simulation at 425 K, the time averaged order parameter (S) was calculated. The calculated S of 0.36 was comparable to the value of 0.4-0.45 found from the experimental data. Apart from providing insight into the relative importance of the various competing forces in the formation of the liquid crystalline phase, these simulations are also expected to be useful in predicting the mesophase behaviour of liquid crystalline systems.     

Blue phase stability of n-OCB homologue chiral nematic liquid crystal mixtures

Blue phase (BP) stability of a chiral nematic liquid crystal (LC) mixture is dependent upon chemical structure as well as physical properties. In this study, the blue phase temperature range dependent on alkyl chain length was investigated in order to evaluate the relationship between blue phase stability and the molecular structures of four kinds of 4-n-alkyloxy-4'-cyanobiphenyl (n-OCB) homologue chiral nematic LC mixtures composed of rod-like nematic LCs. It was confirmed that the blue phase temperature range was strongly dependent upon the molecular parity, K ₃₃/K ₁₁ and the helical twist power of the n-OCB homologues chiral nematic LC mixtures.     

Thermo-recording in (side chain type smectic A liquid crystal polymer/nematic liquid crystal/chiral dopant/dichroic dye) composite with a low power laser

Thermo-recording in a [side chain type smectic A liquid crystal polymer (SmA-LCP)/nematic liquid crystal (N-LC)/chiral dopant/dichroic dye] composite has been realized by using 2mW of power from a He-Ne laser. The laser irradiation-induced phase transitions of smectic A (SmA) → chiral nematic (N*) → SmA formed the dominant thermo-recording mechanism in the composite. Thermo-recording in the (SmA-LCP/N-LC/chiral dopant/dichroic dye) composite exhibited a higher contrast when compared with the non-polymeric (SmA-LC)/N-LC/chiral dopant/dichroic dye composite.     

A novel series of styrene-based liquid crystal monomers displaying either nematic or chiral nematic phases

A new series of liquid crystalline styrene-based monomers is described. These monomers are prepared by the DCC-mediated esterification reaction between 4-[11-(4-vinylphenoxy)undecyloxy]benzoic acid and a range of phenols chosen due to their proven utility in the synthesis of liquid crystals. Most members of the series display thermally stable (enantiotropic) nematic phases, although a few give only monotropic nematic phases. By incorporating the (S)-2-methylbutyl side chain, monomers that exhibit the chiral nematic phase can be obtained. Predictably, monomers derived from phenols containing an additional ring as substituent (e.g. 4-cyano-4'-hydroxybiphenyl) display relatively high transition temperatures. In contrast, monomers derived from simple 4-n-alkylphenols possess a nematic phase, which is accessible at moderate temperatures. In addition, a eutectic mixture derived from these monomers has a melting point only just above room temperature, which is an advantage for the fabrication of robust films via the in situ photopolymerization process. Standard free radical polymerization of a number of these monomers provides side chain liquid crystal polymers, SCLCPs, with mesophases that are stable over a wide temperature range. For a homologous series of SCLCPs containing a terminal n-alkyl chain on the mesogenic group, an unexpected but distinct odd-even effect is observed.     

Non-symmetric chiral nematic liquid crystal dimers containing trifluoromethyl and 1,2-propanediol

ABSTRACT

A series of non-symmetric liquid crystal (LC) dimers with the same chiral core 1,2-propanediol (PD) have been synthesised, termed as ABBA-PD-TFBA, PBBA-PD-TFBA, ABA-PD-TFBA, PBA-PD-TFBA and AA-PD-TFBA, respectively, in which one of the two mesogenic groups, the fluorinated mesogenic unit, was kept fix and the other arm was different. The intermediate compounds and LC dimers were characterised by FTIR, ¹H NMR, differential scanning calorimetry, thermogravimetric analysis, polarised optical microscopy and X-ray diffractometer (XRD). The results of the measurements indicated that ABBA-PD-TFBA, PBBA-PD-TFBA and ABA-PD-TFBA displayed optical activity and enantiotropic chiral nematic phase, and PBA-PD-TFBA was an enantiotropic nematic LC while AA-PD-TFBA was a monotropic LC, displaying both nematic phase and smectic A phase on cooling. The results indicated that PD was able to induce the chiral nematic phase, nevertheless, the rigidity of the mesogenic arm, the flexibility of the terminal group and even the type of the terminal chemical bond played an important effect on the thermal properties of the dimers, and even on the formation of the chiral nematic phase. It is also worth noting that C=C at the terminal helped to stabilise the LC phase.     

Spontaneously modulated chiral nematic structures of flexible bent-core liquid crystal dimers

ABSTRACT

We report the induction of spontaneously undulated chiral nematic structures of liquid crystal (LC) dimers with rigid aromatic molecular arms linked by flexible chains with an odd number of carbons. When a small amount of chiral dopants (CD) are added to the dimers, we find the formation of different stripe textures on cooling 4–10 μm films in the nematic phase. The temperature where the stripes form depends on the film thickness and the direction of the stripes depends on the CD concentrations. We show that the experimentally observed stripes are due to undulation instabilities that spontaneously form as a result of the anomalously small bend elastic constant that prefers director bend instead of twist deformation, the opposite of the situation in usual cholesteric LCs.     

The role of segregation in the polarized emission from polyfluorene embedded in a liquid crystal

Polyfluorene (PFO) embedded in a nematic liquid crystal (LC) matrix is investigated. For low PFO weight contents, a homogeneous dispersion is obtained which displays a strong fluorescence anisotropy along the LC director, indicating a significant alignment of the polymeric chains along this direction. Besides, for relatively high PFO weight contents, phase separation takes place. Under these conditions, the sample is composed of micrometer‐sized domains, where the two species are in solution, enclosed by segregated polymeric boundaries. By polarized‐photoluminescence imaging and spectroscopy, it is found that most of the light emission originates from these boundaries and gets strongly pinned along their orientation. Since boundaries are mainly oriented orthogonal to the LC chains, this morphological alignment results in a system in which the orientation of the polarization emission can be predicted and possibly controlled. Conversely, in the homogeneous sample one can obtain a homogeneous emission polarization by controlling the alignment of the LC. These features are potentially relevant for the development of flexible polarization‐sensitive optoelectronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1558–1563     

Dielectric properties of a strongly polar nematic liquid crystal compound doped with gold nanoparticles

This study focuses on the electrical characteristics of a strongly polar nematic liquid crystal, Hexyloxy-cyanobiphenyl (6OCB), doped with a low concentration (2% by weight) of citrate buffer stabilised gold nanoparticles (GNPs) at low frequencies between 20 Hz and 35 MHz. The doped samples have lower values of nematic–isotropic transition temperature, permittivity (both parallel and perpendicular to the field direction) and dielectric anisotropy; however, relaxation time and activation energy were increased. The observed results could be explained on the basis of weakly anisotropic nature of GNPs and a local rearrangement of liquid crystal molecules surrounding the nanoparticles. Moreover, a complimentary suggestion on a possible change in the dipole–dipole correlation is made to explain the difference in changes (qualitative and quantitative) observed for permittivity of the host nematic liquid crystal doped with GNP. Temperature dependent dielectric relaxation studies indicate an increase in viscosity and potential barrier; and hence a change in strength of inter-molecular and intra-molecular interactions is suggested.     

Memory effects in chiral nematic liquid crystals doped with functionalised single-walled carbon nanotubes

Octadecylamine-functionalised single-walled carbon nanotubes (SWCNTs) were dispersed into nematic liquid crystals (LCs) doped with chiral molecules. The collective orientation of nematic LC molecules in helical layers was manipulated by varying dopant concentration. Highly anisotropic nature of SWCNTs enhanced the anisotropy of the LC as confirmed by polarised fluorescence spectroscopy. The π–π interaction of SWCNTs present in the planar alignment layers and twisted nematic LC molecules affects the molecular relaxation process. An irreversible electro-optic memory in the material has been observed.     

Characterization of large tilt-angle flexoelectro-optic switching in chiral nematic liquid crystal devices

The ‘flexoelastic ratio’ is commonly used to characterise the electro-optic behaviour of chiral nematic liquid crystal (LC) devices that exhibit flexoelectro-optic switching. There has been renewed interest in this electro-optic effect of late as new LC materials and mixtures have been developed that exhibit large tilt angles, Ø, of the optic axis (Ø ≥ 45°) whilst maintaining a fast response time (< 1 ms). In this study, we compare the different flexoelastic ratios that are obtained for fixed and variable-pitch chiral nematic LCs for materials with a tilt of the optic axis as large as Ø = ± 45°. We show that for large tilt angles of the optic axis the values for the two different flexoelastic ratios measurably diverge. Of the two ratios, we propose that for large tilt-angle mixtures it is more appropriate to use the flexoelastic ratio that is derived for the case when the pitch of the helix is constrained. In addition, a simple way of determining the ‘pitch-constrained’ flexoelastic ratio is presented that involves identifying the electric field amplitude at the point for which the transmission levels are the same for both positive and negative electric field polarities.