Smectic-like bâtonnets in nematic/twist-bend nematic biphasic samples

ABSTRACT

We have studied a mixture of the twist-bend nemogenic dimer CB7CB with rod-like nematic molecules, which exhibits nematic (N) and twist-bend nematic (N_TB) phases and a very large biphasic coexistence range. At the N-N_TB transition, we observe the nucleation of highly anisometric N_TB droplets which are very similar to the classic smectic A (SmA) bâtonnets. These observations confirm the recently proposed close analogy between the N_TB and SmA phases, on the basis of their identical macroscopic symmetry. As for their smectic analogues, the N_TB bâtonnets are fluid in two dimensions; they easily merge when brought into contact and they are solid-like in that they did not flow along their optic axis. The observed fluidity and low viscosity show that the N_TB phase is indeed a nematic phase, i.e. an anisotropic fluid, rather than a soft crystal or glassy state. Unlike their smectic analogues, the N_TB bâtonnets have almost perfect symmetry of revolution and the axis of the N_TB helix is uniformly aligned parallel to the long axis of the bâtonnet. The large aspect ratio of the bâtonnets, typically ≈ 10–30, indicates a very strong anisotropy of the N-N_TB interfacial energy, W₂/W₀ ≈ 200–2000, and suggests that the anchoring energy differs from the usual Rapini–Papoular form.     

Virtual isotropic‐nematic transitions in alkyl cyanobiphenyls

Pretransitional fluctuations in the isotropic phase of liquid crystalline and non‐liquid crystalline alkyl cyanobiphenyls have been investigated using light scattering and magnetic birefringence measurements. We find evidence for a virtual isotropic‐nematic phase transition in short‐chain alkyl cyanobiphenyls with no observable nematic phase. The measured temperature dependence of fluctuations is well‐described by mean‐field theory. Virtual phase transition temperatures extrapolated from separate light scattering and magnetic birefringence experiments are in good agreement. Landau–de Gennes model parameters for the compounds investigated are calculated from the experimental results.     

Polar 2‐alkoxyethoxy‐substituted nematic liquid crystals

The synthesis is reported of a series of polar nematic liquid crystals incorporating an alkoxyalkoxy chain attached in a terminal position to a molecular core consisting of two aromatic rings. The dependence of the mesomorphism and phase transition temperatures on the nature of this terminal chain was studied. The shape anisotropy of the core is increased by the presence of an additional 1,4‐disubstituted phenyl unit in a number of p‐terphenyls. A number of highly polar esters with a terminal methoxyethoxy chain have been prepared as dopants to lower the threshold voltage of LCDs. The presence of the methoxyethoxy chain leads to an increase in the molecular dipole moment, the dielectric anisotropy and the dielectric constant perpendicular to the molecular long axis. Several compounds with a four‐unit diether central linkage were also prepared.     

X-ray investigation of the nematic and reentrant nematic phases of N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline

We have performed an X-ray scattering study of the nematic-smectic A and reentrant nematic-smectic A phase transitions in N-[(4-n-octyloxybenzoyloxy)-salicilidene]-4′-cyanoaniline (OOBOSCA). A diffractometer with a linear position sensitive detector was used. The results show that the smectic phase in OOBOSCA is of the A_d type with an interlayer spacing incommensurate with the molecular length L; d ∽ 1·2L. In the reentrant nematic phase two types of fluctuation modes were found. One of them corresponds to the monolayer wavevector q ₁ ∽ 2π/L, and the other is due to the partial bilayer fluctuations with the wavevector q ₂ ∽ 0·8q ₁. The temperature dependences of the interlayer spacing, X-ray scattering intensity and longitudinal correlation length for both types of layering in the reentrant nematic phase are presented. The change of the fluctuation regime from S_Ad, to S_Cd type with decreasing temperature in the reentrant nematic phase of OOBOSCA was found. The results are discussed on the basis of models with competing order parameters. The influence of alkyl chain flexibility on the stability of a partial bilayer smectic phase is also considered.     

Apolar 2‐alkoxyalkoxy‐substituted nematic liquid crystals

The synthesis is reported of a series of apolar nematic liquid crystals incorporating an alkoxyalkoxy chain attached in a terminal position to the molecular core. The dependence of the mesomorphism and phase transition temperatures on the nature of the terminal chain with one, two or three oxygen atoms was studied. Some compounds with a completely alicyclic molecular core and a terminal 2‐methoxyethoxy chain exhibit a nematic phase with a low melting point, birefringence and viscosity and a relatively high clearing point in the absence of smectic phases. They do not to absorb light in the near UV and may be useful as components of UV‐stable nematic mixtures for use in photoluminescent liquid crystal displays. The presence of the methoxyethoxy chain leads to a relatively large dipole moment perpendicular to the molecular long axis.     

Third order optical non–linearities of nematic liquid crystals

Abstract

Liquid crystals can exhibit large third order optical non-linearities. Using the Z-scan technique, we have measured the intensity dependence of the non-linear absorption and non-linear refractive indices on time-scales ranging from milliseconds to picoseconds for nematic liquid crystals. This method allows the determination of the non-linear absorption coefficients as well as the signs and magnitudes of the non-linear refractive indices for different polarizations. A two pulse technique further enables estimation of the response time of the dominant mechanism. Using CW argon and Q-switched and mode-locked pumped dye lasers, we have carried out Z-scan measurements on aligned liquid crystal samples as a function of temperature, as well as wavelength. In the geometries studied, director reorientation is not expected to take place. On the nanosecond time-scale, all materials studied were self-focusing for polarization perpendicular to the director, and self-defocusing for parallel polarization. On the picosecond timescale, the samples were self-focusing for all polarizations, but strong non-linear birefringence was typically observed. An attempt is made to relate the bulk response to the molecular structures.     

Thermotropic biaxial nematic liquid crystals: spontaneous or field stabilized?

An intermediate nematic phase is proposed for the interpretation of recent experimental results on phase biaxiality in bent-core nematic liquid crystals. The phase is macroscopically uniaxial but has microscopic biaxial, and possibly polar, domains. Under the action of an electric field, the phase acquires macroscopic biaxial ordering resulting from the collective alignment of the domains. A phenomenological theory is developed for the molecular order in this phase and for its transitions to purely uniaxial and to spontaneously biaxial nematic phases.     

Liquid crystalline organic semiconductors: nematic spiro[cyclopentyl-1,9′]fluorenes

A number of nematic spiro[cyclopentyl-1,9′]fluorene reactive mesogens with polymerisable oxetane or non-conjugated diene end-groups have been successfully synthesised. The melting and clearing points of these new spiro[cyclopentyl-1,9′]fluorenes are much higher than those of the corresponding 9,9-diethyl- or 9,9-dipropyl-substituted fluorenes, which are present in many light-emitting polymers currently used in polymer light-emitting diodes. The significant difference in transition temperature may be attributed to the lower intermolecular separation induced by the more rigid and less bulky cyclopentyl group, confirmed by molecular modelling. The presence of either these short but flexible aliphatic chains, or a rigid alicyclic group of similar size and shape, results in only small differences in the photoluminescence spectra and efficiency of these model liquid crystalline organic semiconductors, and in their improved thermal stability.     

Symmetrical carbazole–fluorene–carbazole nematic liquid crystals as electroluminescent organic semiconductors

A series of novel symmetrical carbazole–fluorene–carbazoles has been synthesised using simple and highly efficient reaction pathways. The correlation between their molecular structures, differing in the length of the alkyl chains in the lateral position attached to a 2,7-disubstituted fluorene moiety in the molecular core and/or differing in the length of alkoxy chains at the terminal positions of 2,7-disubstituted carbazole moieties, was investigated. Their mesomorphic behaviour, transition temperatures, energy levels and band gaps were measured. A test organic light-emitting diode incorporating one of these compounds exhibits blue electroluminescence.     

Exact tilt angle profiles for splay–bend deformations in nematic liquid crystals

The exact tilt angle profiles for splay–bend deformations, in nematic liquid crystal samples limited by inhomogeneous surfaces, are determined in the one‐constant approximation. The boundary value problem concerning the situation of strong anchoring at the surfaces of a sample of slab shape of thickness d (Dirichlet's problem) is analytically solved in the presence of an external uniform field. The boundary value problem concerning the weak anchoring situation (mixed problem) is also exactly solved in the absence of an external field. The results are used to obtain the thickness dependence of the optical path difference between the ordinary and extraordinary rays, from which the physical properties of the sample can be deduced.     

Synthesis and mesomorphic behaviour of wedge‐shaped nematic liquid crystals with flexoelectric properties

The synthesis and mesomorphic behaviour of a series of wedge‐shaped liquid crystals and some reference compounds are reported. These unusual liquid crystals possess smectic C, smectic A and nematic phases. These new wedge‐shaped materials with a high degree of shape anisotropy and a large dipole moment can be used to induce an increase in the flexoelectric effects of nematic guest–host mixtures as dopants at low concentrations.     

Nonlinear optical properties of dye-doped E7 liquid crystals at the nematic–isotropic transition

This work shows the influence of a 2,1,3-benzothiadiazole-based dye in the nonlinear optical refraction and nonlinear optical absorption of the thermotropic liquid crystal E7 at the nematic–isotropic transition in the ms time-scale using the Z-scan technique. The addition of dye does not modify the critical exponent of the nonlinear birefringence observed for the undoped sample at the transition, confirming the tricritical character. Also, the order parameter based in the nonlinear absorption shows, for the samples with higher dopings, a critical exponent that deviates from the expected value in the tricritical hypothesis.     

Influence of the anisometry of magnetic particles on the isotropic–nematic phase transition

The influence of the shape anisotropy of magnetic particles on the isotropic–nematic phase transition was studied in ferronematics based on the nematic liquid crystal (LC) 4-(trans-4-n-hexylcyclohexyl)-isothiocyanato-benzene (6CHBT). The LC was doped with spherical or rod-like magnetic particles of different size and volume concentrations. The phase transition from isotropic to nematic phase was observed by polarising microscope as well as by capacitance measurements. The influence of the concentration and the shape anisotropy of the magnetic particles on the isotropic–nematic phase transition in LC are demonstrated here. The results are in a good agreement with recent theoretical predictions.     

Reentrant nematic phase in 4-alkyl-4′-cyanobiphenyl (nCB) binary mixtures

The appearance of reentrant nematic phase was identified in nCB/8CB (n = 1–6) binary mixtures using differential scanning calorimetry, small-angle X-ray diffraction and polarising microscopy with photomonitor. Phase diagrams can roughly be unified if plotted against the average number of alkyl chain length. Distinction was recognised for the phase boundaries between nematic and smectic A phases of even and odd n of the minor component nCB. The character of 8CB as ‘SmA former’ is briefly discussed.     

The twist-bend nematic phase: molecular insights from a generalised Maier–Saupe theory

ABSTRACT

Bent-shaped liquid crystal dimers exhibit a non-conventional nematic phase, which in the last few years has been actively investigated. A structural model of this phase has been proposed, which is characterised by a helical modulation with a periodicity of the order of few molecular lengths. Such a model, which is generally denoted as twist-bend nematic (N_TB), is consistent with various experimental evidences and is supported by theories and simulations. Here, we will examine in more detail the features and the implications of a generalised Maier–Saupe theory, which was recently proposed to explain the origin and structure of the N_TB phase. In particular we will analyse the relevant molecular order parameters, with special attention to the polar and biaxial ones, and we will discuss the concept of ‘tilted director’, which may give rise to some ambiguity. The phase behaviour will be described as a function of the bend angle between the mesogenic moieties of a dimer, which in the generalised Maier–Saupe theory is the key molecular feature. Extension of the theory to include fluctuations of the bend angle will allow us to examine the effect of the molecular flexibility on the phase diagram.     

Surface anchoring of nematic liquid crystal 8OCB on a DMOAP‐silanated glass surface

Dynamic light scattering spectroscopy has been used to determine the temperature dependence of the anchoring strength of the nematic liquid crystal 8OCB on DMOAP‐silanated glass surfaces inducing homeotropic alignment. Wedge‐type glass cells with known thickness profile starting from 150 nm to several microns have been used in the experiments. The relaxation rates of the nematic fluctuations with the wave vector perpendicular to the confining surfaces have been measured as a function of the cell thickness. Fitting of the thickness dependence of the relaxation rate allows for straightforward determination of the surface extrapolation length and therefore also the strength of the surface anchoring, which is 1×10^?4 J m^?2. The overall experimental accuracy of the experiments is discussed.     

Influence of underlying local organisations in typical nematic phase of 6CHBT and induced nematic phase of bicomponent liquid crystalline systems 4DBT–12CB – a Fast Field Cycling NMR investigation

Variable-temperature proton magnetic relaxation dispersion (PMRD) profiles are collected in the induced nematic phases of the binary liquid crystalline mixtures composed of smectic mesogens: 5-butyl-2-(4-isothiocyanatophenyl)-1,3-dioxane (4DBT) and 4′-dodecyl-4-cyanobiphenyl (12CB) and the low viscous nematogen 4-(trans-4′-n-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT), with a view to assess the influence of local organisations on the power spectrum of director fluctuation modes. Two distinct compositions of the binary mixture i.e. 50 mol% of 12CB (without a smectic phase) and 70 mol% of 12CB (with a smectic phase) are used. Fast Field Cycling nuclear magnetic resonance relaxometry is employed to measure proton spin-lattice relaxation rates (R₁) as a function of Larmor frequency (10 kHz–30 MHz). PMRD data analysis with the choice of a suitable model indicated nematic clusters of moderate size (~200 Å) found in the broad nematic region of 50 mol% 12CB, whose size is almost invariant with temperature. On the other hand, cybotactic clusters, i.e. local smectic organisations of relatively larger size (~2000–3000 Å), are observed near the nematic–smectic transition (T > T_AN) of 70 mol% 12CB. Interestingly, the shape geometry of such local organisations accessed from PMRD analysis is weakly anisotropic near T_AN, while being isotropic near T_NI for 70 mol% 12CB.     

X‐ray diffraction from the uniaxial and biaxial nematic phases of bent‐core mesogens

X‐ray diffraction patterns for the uniaxial and biaxial nematic phases exhibited by rigid bent‐core mesogens were calculated using a simple model for the molecular form factor and a modified Lorentzian structure factor. The X‐ray diffraction patterns depend strongly on the extent of the alignment of the molecular axes as well as the orientation of molecular planes. The X‐ray diffraction can be unequivocally used to identify the biaxial nematic phase, study the uniaxial–biaxial phase transition, and estimate the order parameters of the nematic phase.     

Shift of the nematic–isotropic phase transition temperature in a thin layer of a metallomesogenic complex

The effect of boundaries on the nematic–isotropic phase transition temperature in a melt of a metallomesogenic complex was studied for the first time. This was done by comparison of the electro-optical constant of the isotropic phase with the dielectric and optical anisotropy of the nematic phase on the basis of the Landau–de Gennes theory. In a real experiment, the two liquid phases (nematic and isotropic ones) coexist in a range of several degrees around the transition. According to polarization microscopy data, the phase transition temperature decreases by more than 10°C as the metallomesogen layer thickness is reduced from 200 to 5 μm.