Terahertz properties of fluorinated liquid crystals

In this article, optical properties of four fluoro-substituted 4-propyl-4′-[(4-ethylphenyl)ethynyl] biphenyls and liquid crystal mixture A are presented in the terahertz (THz) range. Birefringence, refractive indices and absorption coefficients for ordinary and extraordinary ray of liquid crystals are described in the range of 0.3 to 3.0 THz. It shows that the measured parameters are dependent on the number and placement of fluorine atoms in the molecules. Measurements have been performed using time-pulsed spectroscopy.     

The effect of phenyl ring on the physical properties of liquid crystals containing 4-pyridyl terminal group

ABSTRACT

Liquid crystals with 4-pyridyl end group containing one triple bond and phenylenes have been synthesised. Their structures were confirmed by traditional spectroscopic methods. The properties were measured by differential scanning calorimetry (DSC), polarising optical microscopy (POM), Abbe refractometer and an electrical constants instrument. The results show that all of the compounds exhibit nematic phase. The addition of a phenylene to the molecular skeleton brings about an obvious increase of the mesophase intervals (from 8.8 to 95.5) and birefringence (up to 0.33), as well as minus or plus effect of dielectric anisotropies depending on the position of the phenylene. Density Functional Theory (DFT) calculations of molecular conformation, polarisability and dipole moment were used to further study the molecular structure–property relationship.     

Electrooptical properties of new type fluorinated phenyl-tolane isothiocyanate liquid crystal compounds

A series of 4?-(4-alkyl-phenyl)-2?,6?-difluorotolane isothiocyanate liquid crystal (LC) compounds were synthesised, and their phase transitions and electrooptical properties were investigated. These compounds exhibit high birefringence, about 0.47–0.52. As the number of carbon atoms in the alkyl chains increases, these LC compounds can exhibit smectic phases. When these LCs were mixed into the commercial LCs, the birefringence values of LC mixtures become higher than pure commercial LCs, and the visco-elastic coefficients of five LC mixtures are very close to each other at every test temperature. The results of response properties indicate that the compounds with a tri-fluorine substitution and n-propyl end group possess better response performance than the others. These LC compounds are particularly attractive for achieving fast response times in LC optic devices.     

Synthesis and mesomorphic properties of chiral fluorinated liquid crystals

Some fluorinated chiral liquid crystals were synthesized and the compounds characterized by IR, ¹H NMR, ¹⁹F NMR and mass spectroscopy and elemental analysis. Their phase transition behaviour was investigated by differential scanning calorimetry and polarizing optical microscopy. Nearly all of the compounds synthesized are liquid crystals with an enantiotropic cholesteric phase. Some of them exhibit a blue phase. Lateral tetrafluoro substitution decreases the clearing point and molecular polarity affects the formation of liquid crystalline phases.     

Synthesis and evaluation of dinaphthylacetylene nematic liquid crystals for high-birefringence materials

We synthesised 1,2-bis(6-alkoxy-2-naphthyl)acetylene as a new dinaphthylacetylene liquid crystal (LC) compound with alkoxy tails of length m (DNA–OCm) and characterised their phase behaviour by polarising optical microscopy and differential scanning calorimetry, where all compounds exhibited a nematic phase. Also, we measured the actual, and not extrapolated, Δn values of this target compound, and our results show the birefringence potential of the pure LC compound. They have high birefringence values, with the highest value of approximately 0.5 obtained for DNA–OC2 at 550 nm at 10°C above the nematic?crystal transition temperature.     

Synthesis and characterisation of imidazolium-based ionic liquid crystals bearing a cholesteryl mesogenic group

A series of cholesteryl-containing imidazolium chlorides and imidazolium tetrachloroaluminates were synthesised, and the chemical structure, liquid crystalline behaviour and ionic conductivity were characterised by several technical methods. Whereas the imidazolium chlorides show chiral smectic A (SmA*) phase on heating and cooling cycles, the imidazolium tetrachloroaluminates display chiral nematic (N*) phase, which is uncommon for ionic liquid crystals (ILCs). The imidazolium chlorides display similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than the different alkyl substituent groups. The imidazolium tetrachloroaluminates show lower melting point temperatures and lower clear point temperature than the imidazolium chlorides. The mesophases exist at rather moderate temperatures. Non-mesomorphic imidazolium tetrachloroaluminate(III) salts with short alkyl substituents have been known for a long time, and the synthesised imidazolium tetrachloroaluminates are the first examples of tetrahalogenoaluminate(III)-containing ILCs. For the imidazolium tetrachloroaluminates, imidazolium cations combine loosely with AlCl₄^? ions because AlCl₄^? ions are large and occupy more space in spite of the hydrogen bond and electrostatic attraction interaction, indicating that the layer structure can be destroyed easily to form N* phase on heating.     

The birefringence and extinction coefficient of positive and negative liquid crystals in the terahertz range

Birefringence and extinction coefficients of positive nematic liquid crystal (NLC) MLC-2142 and negative NLC BHR28000-400 are measured by terahertz time-domain spectroscopy system (THz-TDS). Frequency ranging from 0.1 to 0.6 THz, the birefringence of positive NLC MLC-2142 increases with the increase of frequency, and keeps larger than 0.23, which exhibits application potential in tunable broadband LC THz device where a large birefringence is required. In contrast, the birefringence of BHR28000-400 decreases with the increased frequency, which shows a completely different optical property from the positive NLC. The extinction coefficient of the above two kinds of liquid crystals are also investigated.     

Novel diphenylacetylene-based room-temperature liquid crystalline molecules with alkylthio groups,and investigation of the role for terminal alkyl chains in mesogenic incidence and tendency

In this study, we offer a new family of alkylthio-containing diphenylacetylene-based liquid crystalline molecules (the so-called tolanes) showing nematic phases stable down to room temperature and high birefringence, with insights into the role for terminal alkyl chains in mesogenic incidence and tendency. A number of asymmetric tolane homologues having various alkyl chain lengths in the alkylthio and alkyl groups at each p-, p’-position were synthesised, and their phase transition behaviour was investigated by polarising optical microscope observation, differential scanning calorimetry and wide-angle X-ray diffraction measurement. Consequently, several homologues exhibited monotropic nematic or highly ordered smectic (soft crystal) phases stable down to room temperature. It is found that a long alkyl group on the side opposite to an alkylthio group is prerequisite for mesogenic incidence. In addition, a nematogenic homologue exhibited a higher birefringence value of 0.20 compared to that of 0.19 for an alkoxy counterpart.     

Gravitational field-induced orientational transition of aligned nematic liquid crystals

We demonstrate induced orientational transition of liquid crystal (LC) E7 between two optical fibre tips in a gravitational field as a result of minimising the free energy. The LC orientational transition is from a homeotropic state, with respect to fibre tip, to a tilted state as the spacing between two fibre tips is increased. The orientational distortion introduces birefringence in the optical fibre that changes the polarised direction of the output light. At short spacing, the undistorted homeotropic orientation of LC is preferred. However, at longer spacing, a distorted orientation is preferred. Once the LC director profile is known, a Finite Difference Time Domain method is used to calculate the optical properties, which agree well with the experimental results.     

Synthesis and mesomorphic properties of four-ring fluorinated liquid crystals with trifluoromethyl group

The discovery of nematic phase in 3-fluoro-4-trifluoromethyl-4?-(4?-alkyl [trans, trans-1,1?-bicyclohexyl]-4-yl) 1,1?-biphenyls (n = 2, 3, 4, 5) is an accidental affair. A convenient method was used for the synthesis of these target compounds. After the preparation of the intermediate with trifluomethyl group, the target compounds were synthesised by Suzuki cross-coupling reaction. Then, these phase transition temperatures were measured by polarising textural observation, which confirmed the existence of single nematic phase. These temperatures were also measured by differential scanning calorimetry, which showed that the clearing point of compound (n = 3) is 267℃. The possible mechanism of occurrence of unique nematic phase was discussed on the basis of the principles of fluorine chemistry.     

Experimental studies on the phase diagram and physical properties of mixture of calamitic and discotic nematic liquid crystals

Physical studies on mixture of calamitic and discotic nematic liquid crystals are meagre although they are potential for optimising physical properties. Here, we report experimental studies on the phase diagram and physical properties of mixtures of ambient temperature discotic and calamitic nematic liquid crystals. A substantial decrease in several physical properties such as birefringence, dielectric anisotropy and elastic constants are observed with increasing wt% of discotic compound. On the other hand a large increase in the rotational viscosity is observed. Based on the experimental results a simple model of mutual orientation of the rod-like and disc-like molecules is proposed.     

The synthesis of liquid crystalline lanthanide complexes and their magnetic birefringence

Liquid crystalline complexes of the type [ML(LH)₂](NO₃)₂, where LH=C₇H₁₅O-C₆H₃(OH)CH=N-C₁₈H₃₇ and M=Gd, Dy, and La, have been obtained. All of them exhibit the S_A phase and have high magnetic birefringence constants due to the association of the complexes in solution. In the case of the dysprosium derivative, the effect is much stronger (four orders of magnitude greater than the usual value) because of the high magnetic anisotropy of the particles of the complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1003–1005, June, 1994.The authors are grateful to Prof. S. G. Vul'fson for helpful advice and discussions.     

Effective electrically tunable infrared reflectors based on polymer stabilised cholesteric liquid crystals

Electrically tunable infrared (IR) reflectors based on polymer stabilised cholesteric liquid crystals (PSCLC) have been fabricated. The influence of polymerisation time on bandwidth broadening and response time of the IR reflector was investigated. Such IR reflector can reflect broad band of infrared light from 725 to 1435 nm upon application of a DC electric field, while remaining predominantly transparent in the visible region, with the transmittance in the region of 400–700 nm being above 90%. Bandwidth broadening was induced using low operational power with acceptable switching speeds. Model tests reveal that this IR reflector can effectively control the indoor temperature. The distinct properties of such IR reflector make it a good candidate for smart windows of automobiles and buildings to control interior temperature and save energy.     

Experimental investigation of liquid crystals in the millimetre frequency range

Dielectric properties of n·CB (n = 5, 6, 7, 8) liquid crystals (LCs) are investigated in the frequency intervals of 50–80, 120–160 GHz, and at 0.6 THz. The measurements are carried out in the millimetre wave range by the resonance method and with use of a reflectometer designed on the basis of a Michelson interferometer and quasi-optical metal-dielectric waveguides. Of most interest are the room temperature measurements of the birefringence of LCs. These measurements show that LCs can be used as polarisation transformers in the short wavelength region of the millimetre wave band and the long wavelength region of the sub-millimetre wave band.     

Low loss liquid crystals for infrared applications

Seven fluorinated and chlorinated terphenyl compounds intended for mid-wave infrared (MWIR) applications are synthesised and two eutectic mixtures formulated, and their physical properties evaluated. In addition to low absorption, some desirable properties for MWIR applications include wide nematic range, high birefringence, large dielectric anisotropy and low viscosity. The fluorinated terphenyl mixture exhibits a relatively low absorption in the vicinities of λ ~ 3 μm, but a fairly strong overtone appears in the 4–5 μm region. To suppress these overtone absorptions, short-chain chlorinated terphenyl compounds are proven to be useful.     

Synthesis and the effect of 2,3-difluoro substitution on the properties of diarylacetylene terminated by an allyloxy group

A series of 2,3-difluoro tolane allyloxy-based liquid crystals (LCs), which are composed of the tolane unit, lateral fluoro substituents, alkoxy and allyloxy terminal groups, were synthesised with 4-bromo-2,3-difluorophenol as the starting material via a five-step reaction. Their structures were confirmed by infrared spectroscopy (IR), mass spectroscopy (MS) and nuclear magnetic resonance (NMR). The mesomorphic properties were investigated by differential scanning calorimetry (DSC) and polarising optical microscopy (POM). The dielectric measurement was performed using an independent analyser EC-1 and the birefringence was determined using an Abbe refractometer. The results reveal that LCs have large negative dielectric anisotropy and high birefringence, which are potentially important for the fast response displays and liquid crystal photonic devices (LCDs).     

High birefringent reactive discotic liquid crystals based on asymmetrical triphenylene with phenyl-acetylene moieties

Triphenylene (TP)-based liquid crystals, a category of discotic liquid crystals (DLCs), are easy to synthesise, thermally stable and can undergo self-assembly. A new DLC compound, 2,7,10-tris[4-(6-acryloyloxyhexyloxy)benzoate]-3,6,11-tris[(4-hexylphenyl)ethynyl]-triphenylene, was obtained with a 49% yield using catechol as a starting material and features acetylene groups on its TP core. This material can form films with high birefringence through its cross-linkable acrylate ends. Here, we synthesised this new compound and characterised it using nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis. The thermal behaviour was also investigated using differential scanning calorimetry and polarised optical microscopy. This new asymmetric TP-based DLC compound exhibited a nematic liquid-crystalline phase between ?20 and 170°C and formed an optical anisotropic film with a high birefringence (Δn = 0.21–0.25).     

Imidazolium‐based polymerized ionic liquid crystals containing fluorinated cholesteryl mesogens

A series of polymerized ionic liquid crystals (PILCs) bearing fluorinated cholesteryl mesogens were synthesized in this work, which include polymerized imidazolium bromides (PIBs) and polymerized imidazolium hexafluorophosphates (PIHs). The PIBs were synthesized using alkyl bromine‐containing polysiloxanes and 1‐butyl‐1H‐imidazole, and the PIHs were synthesized by anion metathesis reaction using the corresponding PIBs and KPF₆. The chemical structures, liquid crystalline (LC) properties, and electrorheological (ER) effect of these PILCs were characterized by use of various experimental techniques. All the PILCs showed smectic A mesophase on heating and cooling cycles. The smectic layer structure of these PILCs are originated from the rigid fluorinated cholesteryl mesogens and the flexible moieties in the LC phase, but the ion pairs (imidazolium cations–PF₆^?, Im⁺–PF₆^?; or imidazolium cations–Br^?, Im⁺–Br^?) can disperse in the polysiloxane matrix and expand the d‐spacing in the smectic layers. The PIHs show lower T_g and T_i than the corresponding precursor PIBs, which is due to the larger ion volume of Im⁺–PF₆^? for PIHs than that of Im⁺–Br^? for PIBs. A series of 40 V% ER fluids were prepared by mixing the PILCs with polydimethylsiloxane (PDMS), and the ER behaviors were studied. All the PILC/PDMS fluids showed ER effect, and the PIH/PDMS fluids show a little greater ER effect than the PIB/PDMS fluids. The PILC droplets in the ER fluids become deformed owing to both the orientation of fluorinated cholesteryl mesogens and the suppression of ionic migration when a DC electric field was applied, resulting in the occurrence of ER effect. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and physical properties of high birefringence phenylacetylene liquid crystals containing a cyclohexyl group

We have synthesized new phenylacetylene-based liquid crystals containing a cyclohexyl or cyclohexylethyl group and evaluated their physical properties in order to develop a range of materials having high value of birefringence. The cyclohexyl-containing compounds exhibited nematic behaviour near room temperature and moderate values of δn of around 0.3. The cyclohexylethyl-containing compounds had a very wide nematic range with a high T_NI and very high values of δn of over 0.4. They also exhibited low viscosities. The order parameter was not affected by introducing either a cyclohexyl or a cyclohexylethyl group and the values of δn based on calculated polarizabilities were obtained experimentally.     

Novel high birefringence bistolane liquid crystals with lateral fluorosubstituent

Twelve compounds based on lateral fluorinated bistolane moieties with cyano or trifluoromethyl terminal groups were synthesised with Hagihara–Sonogashira cross-coupling reaction. The molecular structures of the compounds were confirmed by Fourier transform infrared, ¹H-nuclear magnetic resonance and mass spectrometry. The transition temperatures, optical textures and optical anisotropies were determined by differential scanning calorimetry, polarizing optical microscopy and ultraviolet microscopy. The effects of the terminal substituents and lateral fluorosubstituent group on their physical properties were investigated and discussed. The compounds with lateral double fluorosubstituent and cyano terminal group exhibited nematogenic texture, while other compounds showed smectic phase. All the compounds exhibited wide liquid crystal temperature ranges and high clearing points. Interestingly, the compounds have the high birefringence in the range of between 0.480 and 0.633.