Liquid crystalline behaviour of hydrogen-bonded complexes of alkoxycinnamic acids with octyloxystilbazole

Hydrogen-bonded liquid crystalline complexes have been obtained through 1:1 (molar ratio) complexation of 4-n-alkoxycinnamic acids (nCNA: n = 4, 8, 10, 12, where n is the number of carbons in the alkyloxy chain) and trans-4-octyloxystilbazole (8Sz). These hydrogen-bonded complexes (nCNA8Sz) form stable mesophases. The mesomorphic range was extended by the mixing of complexes. Hexatic modification of smectic B (SmB_h), smectic C (SmC), smectic A (SmA), and nematic mesophases of these complexes were determined by a combination of X-ray diffraction and polarizing optical microscopy. Transitions between the various smectic phases were deduced from the temperature-dependent layer spacing of nCNA8Sz. The layer spacing of these complexes in the SmB_h and SmA phases gradually increased with increasing alkoxy chain length. The favouring of smectic phases in these complexes is believed to originate from the increment of polarity of the mesogen by intermolecular H-bonding.     

Liquid crystal dimers containing Cholesteryl and Triazole-containing mesogenic units

ABSTRACT

New liquid crystals categorised as cholesteryl dimers have been successfully synthesised through the reaction between cholesteryl 4-(prop-2-ynyloxy)benzoate moieties with n-azido(cholesteryloxy-carbonyl)alkane. All the dimers display enantiotropic mesophases. Whilst the odd-numbered dimers exhibit chiral nematic (N*), twisted grain boundary (TGB) and chiral smectic C (SmC*) phases, the even-numbered members from the same series show chiral smectic A and C. A detailed inspection on mesophase reveals that the chiral centres and the bent conformation of the odd-numbered members are essential for the induction of TGB phase. However, upon decreasing the temperature, the ratio of the transition temperatures (T_SmC*-SmA*/T_SmA*-I) is found to be 0.95, which indicate the second order transition according to the McMillan’s molecular theory. In addition, the X-ray diffraction study supports the presence of the smectic A phase on the even members rather than the N* by the appearance of the Bragg diffraction peaks at 190°C. A comparison study with the other analogues in which the cholesterol entity is substituted by azobenzene or biphenyl tails has been carried out to assess the relationship between the molecular structure and mesomorphic behaviour.     

Direct transition from the SmA phase to the tilted hexatic phase in liquid crystals with several lactate units

Compounds with differing numbers of lactate units in the chiral part were synthesized. For all materials, at least two smectic phases were found. In addition to the SmA, the SmC* and/or the tilted hexatic SmI*(F*) phase appear according to the length of the non-chiral alkyl chain. For the shortest non-chiral chain, a direct transition from the SmA phase to the SmI*(F*) phase has been discovered and studied. For compounds with the 2-(S)-methylbutyl alkyl chain and two lactate units in the chiral part the antiferroelectric SmC*_A phase occurs. The ferroelectric character of the hexatic phase has been confirmed even just below the SmC*_A phase.     

Ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid with non‐fluorinated or semi‐fluorinated alkanes at a chiral terminal chain

Two series of ferroelectric liquid crystals derived from (S)‐2‐(6‐methoxy‐2‐naphthyl)propionic acid, with non‐fluorinated or semi‐perfluorinated alkanes positioned at a chiral terminal chain, have been synthesized and characterized by differential scanning calorimetry, polarizing optical microscopy and electro‐optical measurements. The non‐fluorinated compounds, 1‐hexyl (S)‐2‐{6‐[4‐(4‐alkanoyloxyphenyl)benzoyloxy]‐2‐napthyl}propionates exhibit rich mesomorphism—the BP_II, N*, TGB_A*, SmA* and SmC* phases. The fluorinated compounds display only the SmA* and SmC* phases, suggesting that the fluorination promotes the formation of smectic phases. In addition, the SmA* and SmC* phases of the fluorinated compounds have enhanced thermal stability as compared with the corresponding phases of the non‐fluorinated compounds. The spontaneous polarization (P _s values) for the non‐fluorinated compounds are higher than those of the fluorinated compounds at any reduced temperature below the SmA*–SmC* transition. The electro‐optical responses measured for these compounds in the ferroelectric phase displayed thresholdless, V‐shaped switching.     

Systematic study of the chiral smectic phases of a fluorinated compound

ABSTRACT

Physical properties of the partially fluorinated compound 3F5FPhF, with hockey stick-like molecules, were studied by complementary methods. Apart from the already reported paraelectric SmA*, ferroelectric SmC* and antiferroelectric SmC*_A phases, the presence of the smectic C*_α subphase in the phase sequence was proved by differential scanning calorimetry, polarising optical microscopy, electro-optic and dielectric spectroscopy methods. The temperature dependence of the smectic layer thickness and correlation length of the lateral short-range order was determined by X-ray diffraction. Based on dielectric measurements three relaxation processes were revealed in the antiferroelectric SmC*_A phase (two collective: P_L, P_H and one molecular: s-process), two collective ones (Goldstone and soft modes) were found both in the ferroelectric SmC* phase and SmC*_α subphase while one relaxation process (soft mode) in the paraelectric SmA* phase. The results were compared with that obtained for other structurally similar compounds, and it was shown that even addition of one methylene group to the side chain influences much on the physical properties.     

New side chain ferroelectric liquid crystalline polymers based on (2S, 3S)-2-chloro-3-methylpentanoic acid: synthesis and phase behaviour

The synthesis of four new chiral mesogenic monomers (M₁–M₄) and side chain ferroelectric liquid crystalline polymers containing (2S, 3S)-2-chloro-3-methylpentanoate is described. The chemical structures and phase behaviour of the monomers and polymers obtained in this study were characterised by Fourier transform infrared, proton nuclear magnetic resonance, polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. The selective reflection of light was investigated with ultraviolet/visible (UV/Vis). Their structure–mesomorphism relationships were discussed. M₁ and P₁ all showed a chiral smectic C (SmC*) phase. M₂ and M₃ revealed a SmC* phase and cholesteric phase, while their corresponding polymers P₂ and P₃ revealed a SmC* phase and smectic A (SmA) phase. M₄ only exhibited a cholesteric phase, whereas the corresponding polymers P₄ showed a SmA phase. Moreover, the selective reflection of light shifted to the long-wavelength region at the SmC* phase range and to the short-wavelength region at the cholesteric range with increasing temperature, respectively. The results seemed to demonstrate that the tendency towards melting temperature (T_m), glass transition temperature (T_g), isotropic temperature (T_i) and mesophase range for the monomers and polymers increased by increasing the mesogenic core rigidity or the number of phenyl ring. The polymerisation effect could lead to higher liquid crystalline to isotropic phase transition temperature, wider mesophase range and more ordered smectic phase formed. In addition, all the obtained polymers had a very good thermal stability and the corresponding T_d increased by increasing the number of phenyl ring.     

Alpha sub-phase in a new ferroelectric fluorinated compound

Dielectric and DSC methods were used to study a new fluorinated liquid crystalline compound exhibiting ferroelectric and paraelectric phases as well as an intermediate alpha sub-phase. Two dielectric relaxation processes were revealed in the SmC* phase: a typical Goldstone mode over the whole temperature range and a soft mode in the pre-transition region on both sides of the SmC*–SmA* transition. From the temperature dependencies of the dielectric increments and critical frequencies for the dielectric relaxation processes observed in all the liquid crystalline phases, as well as from texture observations, it was shown that there is a SmC*_α sub-phase between the ferroelectric SmC* and paraelectric SmA* phases.     

Switching and electrical properties of ferro‐ and antiferroelectric phases of MOPB(H)PBC

Switching and dielectric relaxation phenomena were investigated for an antiferroelectric liquid crystal, 4,4‐(1‐methyloctyloxycarbonyl)phenyl]‐4′‐[3‐(butanoyloxy)prop‐1‐oxy]biphenyl carboxylate, exhibiting chiral smectic A (SmA*), smectic C (SmC*) and antiferroelectric (SmC_A*) phases. Spontaneous polarisations, rotational viscosities, relaxation frequencies, dielectric strengths and distribution parameters were determined as a function of temperature. The electric field required for saturation of the spontaneous polarisation increased with a decrease in temperature. In the SmA* phase, only one relaxation mechanism was observed that behaves as soft mode. Two relaxation processes were detected in the SmC* phase. A high‐frequency relaxation process invariant at 2.2 kHz was due to a Goldstone mode, but the origin of low‐frequency relaxation process (1–20 Hz) is unclear; however, it may belong to an X‐mode. The dielectric spectrum of the SmC_A* phase exhibits two absorption peaks separated by two decades of frequency. The low‐frequency peak is related to the antiferroelectric Goldstone mode, whereas the high‐frequency peak originates from the anti‐phase fluctuation of the directors in the anti‐tilt pairs of the SmC_A* phase.     

Synthesis,characterisation, mesomorphic investigation and temperature-dependent Raman study of a novel calamitic liquid crystal: methyl 4-(4′-n-alkoxybenzylideneamino)benzoate

A new series of Schiff base calamitic liquid crystal; methyl 4-(4′-n-alkoxybenzylideneamino)benzoate (MABAB), H_2n+1C _n OC₆H₄C(H)=NC₆H₄COOCH₃ (n = 6, 8, 10, 12, 14, 16) has been synthesised and characterised by elemental analyses, Fourier transform infrared spectroscopy (FT-IR), ¹H and ¹³C Nuclear Magnetic Resonance (NMR) spectroscopy. The mesomorphic properties of these compounds were studied by differential scanning calorimetry (DSC) and polarising optical microscopy (POM). All members of the series exhibit enantiotropic smectic A (SmA) mesophase. Temperature-dependent micro-Raman study of one of the members, MABAB-10 has been employed to identify phase transitions and the molecular rearrangement therein. Analysis of Raman marker bands; C–H in-plane bending, C–C stretching of phenyl rings and –C(H)=N– linking group of core confirms the transitions clearly as observed through DSC and POM. An in situ Raman measurement of C–H in-plane bending mode has also been performed to visualise the molecular changes more clearly. The Raman study gives an evidence of induced co-planarity of rings at Cr→SmA phase transition. The density functional theoretical (DFT) optimisation of monomer, dimer and rotational conformer of MABAB-10 also support the induced co-planarity at Cr→SmA phase transition.     

Liquid-crystalline oxovanadium(IV) complexes accessed from bidentate [N,O] donor salicylaldimine Schiff-base ligands

A series of bis[4-(n-alkoxy)-N-(4′-R-phenyl)salicylideneiminato]oxovanadium(IV) complexes (n?=?6,?10,?14,?16,?18 and R?=?C₃H₇) were prepared and their mesogenic properties were investigated. The mesomorphic behaviors of the compounds were studied by polarized optical microscopy and differential scanning calorimetry. Ligands display SmA/SmC and unexpected nematic mesophases. The complexes bearing longer alkoxy carbon chain (n?=?10,?14,?16, and 18) showed both monotropic or enantiotropic transitions with smectic A and high ordered smectic E phases. However, the complex with shorter carbon chain length (n?=?6) showed monotropic transition with an unprecedented nematic (N) phase. A density functional theory study was carried out using DMol3 at BLYP/DNP level to obtain a stable optimized structure. A square-pyramidal geometry for the vanadyl complexes has been suggested. A ν_V=O stretching value of ～970?cm^?1 corroborated absence of any V?=?O?···?V?=?O interactions. Cyclic voltammetry revealed a quasireversible one-electron response at 0.61?V for the VO(IV)–VO(V) redox couple. Variable temperature magnetic susceptibility measurements of the vanadyl complexes suggested absence of any exchange interactions among the vanadyl spin centers.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz–13 MHz) has been used to analyse the frequency, temperature and bias‐field dependences of the molecular dynamics of a very high‐spontaneous‐polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature‐dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X‐mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*–SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*–SmA phase transition was revealed.     

Calamitic liquid crystals of 1,2,3-triazole connected to azobenzene: synthesis,characterisation and anisotropic properties

Azobenzene-based calamitic liquid crystals, 4-((4-(4-methoxymethyl-1,2,3-triazol-1-yl)phenyl)diazenyl)phenylalkanoates have been isolated and their structures were characterised. The structure–property correlation with respect to the different alkanoyloxy terminal chain (–COOC_nH_2n+1 where n adopts odd numbers ranging from 3 to 15) has also been given attention in the present study. In this series, all compounds exhibit smectogenic properties. The lower homologues shows enantiotropic SmA phase as well as monotropic SmC phase. The higher homologues exhibit homeotropic alignment of smectic phases. These compounds possess very high anisotropic inclination in which the mesomorphic region covers nearly 80°C.     

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic C_a* (SmC_a*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmC_a* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmC_a* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.     

Amplitude and phase fluctuation modes in the smectic Cα* phase of an antiferroelectric compound

Dielectric measurements have been carried out on the chiral smectic C_α (SmC_α*) phase of a MHPOBC analogous compound. Two relaxation modes have been observed in this phase for planar orientation of the molecules. One process has been observed at frequency lower than that of the soft mode of the chiral smectic A (SmA*) phase. This relaxation process is connected with the helicity of the SmC_α* phase. In the high‐frequency region, another relaxation process has been observed in the SmC_α* phase for which bias field dependence is similar to that of the soft mode at the SmA*–SmC* phase transition. The experimental observations are in agreement with a recently proposed dielectric theory for the SmC_α* phase and theoretical dielectric results obtained by numerical simulations. Thus, we report here experimental verification of two theoretically predicted dielectric modes in the SmC_α* phase.     

Synthesis and liquid crystalline investigation of chiral 6-alkoxy-2-naphathoic acid derivatives

A two new series of materials with a chiral fragment derived from ((S)-(─)-2-methyl-1-butanol and 6-alkoxy-2-naphathoic acid as the molecular core was synthesised and investigated. All the homologues exhibited enantiotropic mesomorphism. Chiral smectic C (SmC*), smectic A (SmA) and chiral nematic (N*) phases were observed in different homologues. All the compounds were characterised by spectroscopic and elemental analysis. Thermal investigations and mesophase characterisations for all the compounds were carried out by the combination of DSC and POM analysis. The effects of the central linkage and various terminal normal alkyl chains with its structurally related compounds have been discussed.     

On the phase sequence of antiferroelectric liquid crystals and its relation to orientational and translational order

The substance MHPOBC is the oldest and still most important reference antiferroelectric liquid crystal (AFLC). There is still considerable controversy concerning the correct phase designations for this material and, in particular, about the presence or absence of SmC* in its phase sequence. By means of dielectric spectroscopy and polarizing microscopy, we show that whereas the pure compound lacks the SmC* phase, this phase rapidly replaces the SmC*_β subphase through the reduced purity resulting from temperature-induced chemical degradation which is hard to avoid under standard experimental conditions. X-ray investigations furthermore show that this change in phase sequence is coupled to a decrease in translational order. This explains the large variations in the reported phase sequence and electro-optic behaviour of MHPOBC, in particular concerning the SmC*β phase which has been said to exhibit ferro-, ferri- as well as antiferroelectric properties. It is likely that the sensitivity of the AFLC phase sequence to sample purity is a general property of AFLC materials. We discuss the importance of optical and chemical purity as well as tilt and spontaneous polarization for the observed phase sequence and propose that one of the key features determining the existence of the different tilted structures is the antagonism between orientational (nematic) and translational (smectic) order. The decreased smectic order (increased layer interdigitation) imposed by chemical impurities promotes the synclinic SmC* phase at the cost of the AFLC phases SmC*_α, SmC*_β, SmC*_γ and SmC*_a. We also propose that the SmA* phase in FLC and AFLC materials may actually have a somewhat different character and, depending on its microstructure, some of the tilted phases can be expected to appear or not to appear in the phase sequence. AFLC materials exhibiting a direct SmA* -SmC*_a transition are found to be typical ‘de Vries smectics’, with very high orientational disorder in the SmA* phase. Finally, we discuss the fact that SmC*_β and SmC*_γ have two superposed helical superstructures and explain the observation that the handedness of the large scale helix may very well change sign, while the handedness on the unit cell level is preserved.     

Differences between smectic homo- and co-polysiloxanes as a consequence of microphase separation

This paper compares smectic phases formed from LC-homo- and LC-co-polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo- and co-polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the 'de Vries' type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on approaching the isotropic phase. For the homopolymer the phase transition SmC* to SmA is first order with a significant thickness change, indicating that this phase is not of the 'de Vries' type. This difference in the nature of the smectic phases is probably a consequence of microphase separation in the copolymer, which facilitates a loss of the tilt angle correlation between different smectic layers. This has consequences for the mechanical properties of LC-elastomers formed from homo- and co-polymers. For the elastomers from homopolymers the smectic layer compression seems to be rather high, while it seems to be rather small for the copolymers.     

Alkyl chain self ordering,induction and suppression of mesophase by Cu(II) containing [1,2,3]-triazole-based bidentate salicylaldimine ligands: synthesis,characterisation and X-ray diffraction studies

Some new Cu(II) complexes containing [1,2,3]-triazole-based bidentate salicylaldimine and its analogues with terminal substituent (F, Cl, Br and I) have been synthesieed. All the target complexes and their uncoordinated ligands were elucidated by elemental analysis and spectroscopic techniques (UV-visible, FT-IR, 1D, 2D ¹H and ¹³C-NMR). The polarising optical microscope and differential scanning calorimetry (DSC) have disclosed all complexes and ligands are mesomorphic except the complex without any terminal substituent. The fluoro-substituted complexes with even parity C₁₄H₂₉ and C₁₆H₃₃ exhibit new enantiotropic nematic phase which was absent in their corresponding ligands, whereas the suppression of SmC phase occurred for all complexes with longer C₁₆H₃₃ and C₁₈H₃₇. X-ray diffraction confirmed the existence of SmA, SmC and N phases for complexes and ligands. The other notable feature is that the self-ordering of terminal alkyl chain occurred in SmA and SmC phases of complexes with even terminal alkyl chain ranging from C₁₄H₂₉ to C₁₈H₃₃. Their corresponding ligands exhibit intercalated structure of SmA and SmC phases. The thermal behaviour studies show that the fluoro-substituted triazole-based complexes possess lowest phase transition temperature and more stable as compared to other substituent which decomposed during the isotropisation.     

In situ observation of the pressure-induced mesophase for 4′-n-hexadecyloxy-3′-nitrobiphenyl-4-carboxylic acid

In situ observation of the optical texture, and X-ray patterns of the pressure-induced mesophase seen for 4′-n-hexadecyloxy-3′-nitrobiphenyl-4-carboxylic acid (ANBC-16) was performed under hydrostatic pressures up to 100MPa using a polarizing optical microscope equipped with a high pressure hot stage and a wide angle X-ray diffractometer equipped with a high pressure vessel respectively. It was found that the pressure-induced mesophase (hereafter refered to as ‘X’) appeared at pressures above 60 MPa, and exhibits a birefringent broken-fan or a sand-like texture that remain unaltered in the SmC phase. The POM-transmitted light intensity curve measured on heating clearly showed the Cr₄ → Cr₁ → SmC → ‘X’ → SmA → I transition sequence at 80 MPa. The optical texture and the POM-transmitted light intensity measured during a pressure cycle at 185°C showed a reversible change between the cubic and ‘X’ phases. The WAXD pattern of the ‘X’ phase showed a spot-like pattern, suggesting no layered structure for this phase, and also revealed a substantial decrease in the d-spacing of the low angle reflection at 80 and 100 MPa, compared with the d-spacings of the (0 0 1) reflection of the SmC phase and also the (2 1 1) reflection of the cubic phase. It is concluded from these data that the ‘X’ phase is a birefringent hexagonal columnar phase.     

Combination of molecular rods and half-discs: transition from lamellar to columnar order in multichain mononuclear ortho-palladated metallomesogens

Novel ortho-palladated phenylpyrimidine-1,3-diketonato organyls with successively increasing numbers of alkyl chains were synthesized and investigated by polarizing optical microscopy and X-ray diffraction. A discontinuous transition from a lamellar to a columnar organization is observed, dependent on the number of chains: molecules with four or five chains from smectic phases (SmA, SmC), the related compound with six chains in the molecule is nonmesomorphic, whereas molecules with seven or eight chains form hexagonal columnar mesophases.