A chiral material with a new phase sequence: twist grain boundary smectic C phase-smectic blue phases

A new phase sequence: twist grain boundary smectic C (TGBC) to smectic blue phases (BP_Sm) is observed in a chiral compound (S)- or (R)-1-methyloctyl 3'-fluoro-4'-(3-fluoro-4-hexadecyloxybenzoyloxy)tolane-4-carboxylate. It is the first time that a TGBC phase has been found to occur under smectic blue phases in the absence of the twist grain boundary smectic A (TGBA) phase. These phases are characterized by polarizing optical microscopy, differential scanning calorimetry and X-ray scattering.     

Twist grain boundary and frustrated liquid crystal phases

Research into the structures and properties of frustrated liquid crystal phases continues apace. A number of new twist grain boundary phases have been discovered, of particular interest are those with their rod-like molecules inclined to the layer planes, i.e. the TGBC phases. A new anticlinic TGBC phase has also been discovered complimenting the synclinic TGBC phases. In addition a number of smectic blue phases (BP_Sm) have recently been discovered.     

Blue phases and twist grain boundary phases (TGBA and TGBC) in a series of fluoro-substituted chiral tolane derivatives

A series of fluoro-substituted tolane derivatives: ( R )-1-methylheptyl 3-fluoro-4-(3-fluoro-4- n alkoxybenzoyloxy)tolane-4-carboxylates is reported. Some members of this series exhibit the phase sequence: Cr-SmC*-TGBC-TGBA-BPI-BPII-BPIII-I. The blue phases, the TGBA and TGBC phases and the SmC* phase were characterized in detail by microscopic observation, differential scanning calorimetry, helical pitch measurements, X-ray structural analysis and electro-optical study. The blue phases directly next to the TGBA phase were shown to be a new type of blue phase exhibiting smectic ordering. A commensurate TGBC phase with constant number of slabs per pitch was observed.     

Dielectric spectroscopy of unsymmetrical liquid crystal dimers showing wide temperature range TGBA and TGBC* phases

The electrical properties of frustrated twist grain boundary (TGB) phase are a matter of curiosity. Some studies have indicated the existence of soft and Goldstone modes in TGBA and TGBC* phases respectively. However, the experimental results are still not very conclusive. In the present work, we report dielectric studies of wide temperature range TGBA and TGBC* phases of an optically active dimeric compound 4‐n‐decyloxy‐4′‐(cholesteryloxycarbonyl‐1‐butyloxy) chalcone in the frequency range of 1 Hz to 35 MHz for the planar and homeotropic anchoring of the molecules. Two different relaxation processes have been detected for the planar anchoring of molecules in the TGBA and TGBC^* phases. The soft mode like behaviour is obtained due to tilt fluctuation of molecules in the megahertz region for both TGBA and TGBC* phases. Goldstone mode like behaviour due to phase fluctuation of molecules has been detected for the TGBC* phase in the low frequency region (～200–300 Hz). Activation energies for DC conductivity have also been determined for various phases of the material.     

Chiral dopant induced twist grain boundary phases

A diarylethane alpha-chloro ester was mixed with a chiral dopant of high helical twisting power at variable concentration to study its capability for induction of twist grain boundary phases. With increasing concentration of the chiral dopant, TGBA* and TGBC* phases were observed with a rather broad region of existence. In contrast to homeotropic alignment, planar boundary conditions seem to enhance the phase stability of the TGB phases, resulting in metastable TGB states and phase coexistence with the respective smectic phases. The phase growth of SmA*/SmC* out of the TGBA*/TGBC* state was studied under isothermal conditions as a function of temperature and concentration of the chiral dopant.     

Chiral dopant induced twist grain boundary phases

A diarylethane alpha-chloro ester was mixed with a chiral dopant of high helical twisting power at variable concentration to study its capability for induction of twist grain boundary phases. With increasing concentration of the chiral dopant, TGBA* and TGBC* phases were observed with a rather broad region of existence. In contrast to homeotropic alignment, planar boundary conditions seem to enhance the phase stability of the TGB phases, resulting in metastable TGB states and phase coexistence with the respective smectic phases. The phase growth of SmA*/SmC* out of the TGBA*/TGBC* state was studied under isothermal conditions as a function of temperature and concentration of the chiral dopant.     

Mesogenic Unsymmetric dimers containing cholesteryl ester and tolane moieties

Among unsymmetric oligomesogens, chiral dimers formed by connecting a cholesteryl ester fragment with various aromatic mesogenic cores through a polymethylene spacer have been attracting much attention due to their remarkable thermal behaviour. In particular, dimers containing a diphenylacetylene segment having an alkoxy chain have shown interesting mesomorphic behaviour. In view of this a new series of unsymmetric dimers consisting of a diphenylacetylene moiety having an alkyl chain and a cholesteryl ester unit joined through a paraffinic spacer have been synthesized and their liquid crystalline properties characterized. The lengths of the central methylene spacer (C₃, C₄, C₅ and C₇) as well as that of the alkyl chain (n-butyl, n-pentyl, n-hexyl and n-heptyl) have been varied to establish structure–property relationships. These investigations have revealed that all the dimers exhibit smectic A, twist grain boundary and chiral neamtic (N*) phases with the exception of one of the dimers for which only the N* phase was observed. Some differences in the mesomorphic properties of the unsymmetric dimers containing odd or even parity methylene spacers have been observed. The majority of dimers having an even (C₄) parity paraffinic spacer show a blue phase while the dimers with odd (C₃, C₅ and C₇) parity spacers exhibit the chiral smectic (SmC*) phase. In some cases, the SmC* phase exists well below (?60°C) and above room temperature.     

Unsymmetrical dimers possessing a cholesteryl ester moiety and a difluoro-substituted biphenyl core: synthesis and mesomorphic behaviour

Some new unsymmetrical dimers consisting of a cholesteryl ester moiety, covalently linked to either a 4′-(1,3-difluoro-4-n-octyloxy) biphenyloxy or a 4′-(2,3-difluoro-4-n-decyloxy) biphenyloxy through odd-even parity paraffinic central spacers, have been synthesized and investigated for their mesomorphic behaviour. Except for one, all the dimers exhibit enantiotropic smectic A, twist grain boundary (TGB) and chiral nematic mesophases. Five of the eight unsymmetrical dimers synthesized show a chiral smectic C (SmC*) phase. Interestingly in some of the compounds the SmC* exists over a wide temperature range including room temperature. Among the eight compounds, a dimer having a C₇ central paraffinic spacer and a C₈ alkoxy terminal chain shows an enantiotropic twist grain boundary with SmC* blocks (TGB_C*) phase. It appears that the variation in the length of the spacer has a remarkable influence on the phase transition temperatures as well as on the mesomorphic behaviour.     

Twist grain boundary states in non-chiral smectogen-chiral dopant

The liquid crystalline systems studied consisted of non-chiral mesomorphic esters [the eutectic mixture of 4-n-hexyloxyphenyl 4-n-octyloxybenzoate and 4-n-octyloxyphenyl 4-n-hexyloxybenzoate] and structurally similar chiral dopants (N-arylidene derivatives of S-1-phenyl- and S- 1-benzyl-ethylamine). Twist grain boundary phases occur between the cholesteric and smectic C* or smectic A phases in all the investigated systems. The different structures of these TGB phases (TGBA and TGBC) are proved by small angle X-ray scattering and textural studies. The concentration and temperature ranges of the TGB phases are defined by the twisting power of the chiral dopants and their own mesomorphic peculiarities. The experimental dependences of TGB phase temperature range on cholesteric helical twist are influenced by a ratio change of the optically active and racemic forms of the dopant at a constant total concentration. The results obtained are discussed within Renn's theory.     

A phenomenological model for the undulating twist grain boundary-C* phase

We propose a simple phenomenological model which is able to account for the various twist grain boundary (TGB) phases, including the recently discovered undulating twist grain boundary-C* (UTGB_C*) phase. In the UTGB_C* phase, the smectic C* (SmC*)-like blocks and the grain boundaries separating them undulate to form a two-dimensional square lattice perpendicular to the TGB helix axis. We treat the grain boundaries separating adjacent smectic blocks as interfaces with an anisotropic interfacial tension. At moderate chiral strengths we find a TGB_A-TGB_C-SmC* sequence. As the chiral strength is increased this goes to the sequence TGB_A-UTGB_C*-SmC*. Such sequences have been observed experimentally.     

Optically Biaxial,Re‐entrant and Frustrated Mesophases in Chiral,Non‐symmetric Liquid Crystal Dimers and Binary Mixtures

Sixteen optically active, non‐symmetric dimers, in which cyanobiphenyl and salicylaldimine mesogens are interlinked by a flexible spacer, were synthesized and characterized. While the terminal chiral tail, in the form of either (R)‐2‐octyloxy or (S)‐2‐octyloxy chain attached to salicylaldimine core, was held constant, the number of methylene units in the spacer was varied from 3 to 10 affording eight pairs of (R & S) enantiomers. They were probed for their thermal properties with the aid of orthoscopy, conoscopy, differential scanning calorimetry and X‐ray powder diffraction. In addition, the binary mixture study was carried out using chiral and achiral dimers with the intensions of stabilizing optically biaxial phase/s, re‐entrant phases and important phase sequences. Notably, one of the chiral dimers as well as some mixtures exhibited a biaxial smectic A (SmA_b) phase appearing between a uniaxial SmA and a re‐entrant uniaxial SmA phases. The mesophases such as chiral nematic (N*) and frustrated phases viz., blue phases (BPs) and twist grain boundary (TGB) phases, were also found to occur in most of the dimers and mixtures. X‐ray diffraction studies revealed that the dimers possessing oxybutoxy and oxypentoxy spacers show interdigitated (SmA_d) phase where smectic periodicity is over 1.4 times the molecular length; whereas in the intercalated SmA (SmA_c) phase formed by a dimer having oxydecoxy spacer the periodicity was found to be approximately half the molecular length. The handedness of the helical structure of the N* phases formed by two enantiomers was examined with the aid of CD measurements; as expected, these enantiomers showed optical activities of equal magnitudes but with opposite signs. Overall, it appears that the chiral dimers and mixtures presented herein may serve as model systems in design and developing novel materials exhibiting the apolar SmA_b phase possessing D_2h symmetry and nematic‐type biaxiality.     

Chiral Bent-Shaped Molecules Exhibiting Unusually Wide Range of Blue Liquid-Crystalline Phases and Multistimuli-Responsive Behavior

Recently, an unprecedented observation of polar order, thermochromic behavior, and exotic mesophases in new chiral, bent-shaped systems with a −CH₃ moiety placed at the transverse position of the central core was reported. Herein, a homologous series of compounds with even-numbered carbon chains from n=4 to 18 were synthesized, in which −Cl was substituted for −CH₃ at the kink position and a drastic modification in the phase structure of the bent-shaped molecule was observed. An unusual stabilization of the cubic blue phase (BP) over a wide range of 16.4 °C has been witnessed. Two homologues in this series ( 1 -12 and 1 -14) exhibit an interesting phase sequence consisting of BPI/II, chiral nematic, twist grain boundary, smectic A, and smectic X (SmX) phases. The higher homologues ( 1 -16 and 1 -18) stabilize the SmX phase enantiotropically over the entire temperature range. Crystal structure analysis confirmed the bent molecular architecture, with a bent angle of 148°, and revealed the presence of two different molecular conformations in an asymmetric unit of compound 1 -4. A DFT study corroborated that the −Cl moiety at the central core of the molecule led to an increase in the dipole moment along the transverse direction, which, in turn, facilitated the unusual stabilization of frustrated structures. Crystal polymorphism has been evidenced in three homologues ( 1 -10, 1 -12, and 1 -14) of the series. On the application of mechanical pressure through grinding, compound 1 -10 transformed from a bright yellow crystalline solid to a dark orange–green amorphous solid, which reversed upon dropwise addition of dichloromethane, indicating reversible mechanochromism in this class of compounds. In addition, excellent thermochromic behavior has been observed for compound 1 -10 with a controlled temperature–color combination.     

Dielectric and optical rotatory power investigations of an antiferroelectric liquid crystal 12OF1M7 in a homeotropic cell: implications for models of the structure of ferrielectric phases

The antiferroelectric liquid crystal (AFLC) under investigation possesses different helical smectic phases. Measurements of the optical rotatory power (ORP) of these phases have elucidated the quality of this method for finding the phase transitions between several phases and for investigating their helical structure. The optical rotatory power as a function of temperature for seven wavelengths of light in the range 441 to 665 nm was measured for different phases of the AFLC material investigated, (R)-1-methylheptyl 4-(4'-n-dodecyloxybiphenyl-4-yl-carbonyloxy)-3-fluorobenzoate, with acronym 12OF1M7. The values of the pitch and the optical anisotropy in the plane of the smectic layers for the FiLC (SmC*_FI3) phase and SmC*_Aphase have been calculated from the ORP data. The results of the ORP rule out the simple clock model for describing the structure of the SmC* (SmC*_I1) and AF (SmC*_FI2) phases. The results for these phases can be explained either in terms of the modified Ising model or the highly distorted clock model. The ORP measurements establish the existence of SmC*_FI3 found already from dielectric, polarization and polarized IR spectroscopy.     

New (1R,4R)-2-arylidene-p-menthan-3-ones with a bridging ester group in the arylidene fragment. Synthesis and behavior in liquid-crystalline systems

(1R,4R)-2-(4-Hydroxybenzylidene)- and (1R,4R)-2-(4"-hydroxybiphenyl-4-yl)methylene-p-menthan-3-ones were synthesized by condensation of (–)-menthone with O-tetrahydropyran-2-yl derivatives of 4-hydroxybenzaldehyde and 4"-hydroxy-4-formylbiphenyl, respectively, in a DMSO—base medium followed by the removal of the protective group. The reactions of these hydroxy derivatives with 4-alkylbenzoic, 4-alkyloxybenzoic, trans-4-alkylcyclohexane-4-carboxylic, and 4"-alkylbiphenyl-4-carboxylic acids afforded three series of new chiral esters. Compounds containing the arylidene moiety with three benzene rings were found to exhibit liquid-crystalline properties. The characteristic features of these compounds are discussed based on the results of studies by polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. It was found that the mesomorphic compounds under study can form a smectic A mesophase, twist grain boundary mesophases (TGBA), and blue phases in a wide temperature range. Upon dissolution of certain of chiral compounds in 4"-cyano-4-pentylbiphenyl, a rather high twisting power and the thermal stabilizing effect on mesophases were observed.     

Novel phase behaviour in two (smectic/cholesteric) liquid crystal mixtures

The phase behaviours of mixed liquid crystal systems having either Sm/N or Sm/Ch properties have been studied. The (smectic/nematic) binary system formed smectic phases over a wide and much enhanced range of temperature (42 C) and a broad concentration range (0-90 wt %). The ternary smectic/cholesteric system, in appropriate concentration ranges, exhibited the smectic A phase, a TGBA-like twist grain boundary A phase, the cholesteric phase and blue phases. The TGBA-like phase appeared in the cholesteric-smectic phase transition range. Three textures (chiral pitch, fan-shaped and scale-like) for the cholesteric phase of the ternary smectic/cholesteric mixtures were observed in the ranges 0-7, 7-43 and 43 wt % respectively, of cholesteric CB15, in a binary Sm/N mixture.     

Structure property and mesomorphic behaviour of S-shaped liquid crystal oligomers possessing two azobenzene moieties

A new series of symmetrical S-shaped oligomers 4,4?-bis(ω-2-(ω-[(bromophenyl)diazenyl]-alkoxy)phenoxy)hexylbiphenyl consisting of two different spacers (inner -(CH₂)₆- and outer -(CH₂)_n-) have been synthesised. Their physical, thermal and texture observation over various transition temperatures are reported. The outer spacers for these compounds vary from n = 4 to n = 9. The oligomers with even number of members exhibit monotropic phase in which the compound with n = 4 shows nematic (N) phase whilst those with members n = 6 and 8 exhibit N and smectic A (SmA) phases. However, the homologs with odd number of members display enantiotropic phase in which the compound with n = 5 exhibits N and smectic phases whereas the members with n = 7 and 9 are predominantly smectogenic. The temperature range of N phase for even-numbered member decreased with elongation of the outer spacer. The smectic phase stability among the members in the present series increases when the outer spacer n is increased from 5 to 8.     

A specialized apparatus for the study of liquid crystals at high pressures

Abstract

A pressure system specially designed for the study of liquid crystal materials at high pressures up to 4kbar is presented. The pressure system is based on a hydrostatic screw injector and uses either oil or gas as the pressure transmitting medium. The type of measurements which can be performed with the instrument include polarized microscopy, optical spectroscopy, electrooptic and electrical measurements. The different measurements performed place specific constraints on the design of the apparatus and the pressure cells, and details are given. A preliminary study of the smectic A modification of the twist grain boundary phase (TGB_A) at high pressures is presented. The pressure versus temperature phase diagram shows (i) a negative gradient of the TGB_A/isotropic phase boundary line and (ii) that the TGB_A phase does not exist at pressures above about 250 bar. Following Lubensky's analogy between the TGB_A phase and type II superconductors, the disappearance of the TGB_A phase at high pressure may imply that the Landau-Ginsburg parameter K decreases with pressure.     

Dynamics in ferro- and antiferroelectric phases of a liquid crystal with fluorinated molecules as studied by dielectric spectroscopy

For 1-[3-fluoro-4-(1-methylheptyloxycarbonyl)phenyl]-2-[4-2,2,3,3,4,4,4-heptafluorobutoxybutoxy)biphenyl-4-yl]ethane (1F7), built of chiral molecules, results of dielectric measurements of liquid-crystalline and solid phases are presented. Rich polymorphism of liquid-crystalline (SmC*, SmC*_A and SmI*_A) phases as well as of solid (Cr1 and Cr2) phases were observed down to –130°C. At a frequency range from 0.1 Hz to 3 MHz, the relaxation processes were detected in ferroelectric SmC*, antiferroelectric SmC*_A and highly ordered SmI*_A smectic phases. The mechanism of complex dynamics (moleculear and collective) was identified with the help of the bias field. Vitrification of conformationally disordered crystal phase Cr2 was found in accordance with calorimetric observations.     

Solubility of thioindigo dopants in a smectic liquid crystal host evaluated by 2H NMR spectroscopy

The solubility of two partially deuterated thioindigo dopants in a smectic liquid crystal host was evaluated by variable temperature ²H NMR spectroscopy and polarized microscopy. 2H NMR spectra showed that the dopant (±)-6,6'-bis(2-octyloxy)-5,5-dinitrothioindigo-d ₆ forms a homogeneous solution with the smectic phases of the liquid crystal host (±)-4-(4-methylhexyloxy)phenyl 4-decyloxybenzoate (PhB) up to its saturation point of 3 mol %. These results are consistent with polarized microscopy observations of the dopant crystallizing out of solution upon reaching a concentration of 3 mol %. On the other hand, ²H NMR spectra of (±)-5,5'-dichloro-6,6'-bis(2-octyloxy)thioindigo-d ₆ dissolved in PhB showed evidence of a partitioning of the solution between smectic and isotropic microdomains, which increases with increasing dopant concentration—from 1.2 to 9.1 mol %. To a large extent, this smectic/isotropic microphase separation could not be detected by polarized microscopy. These results suggest that ²H NMR spectroscopy can provide a more accurate determination of the occurrence and extent of microphase separation in doped liquid crystal samples.     

Effect of a lateral substituent on the mesomorphic properties of ferroelectric side chain liquid crystalline polysiloxanes

The synthesis of side chain liquid crystalline polysiloxanes containing oligooxyethylene spacers and ( S )-2-methylbutyl 4-\[(4-oxybiphenyl-4-yl)carbonyloxy]-3-fluorobenzoate mesogenic side groups is presented. Differential scanning calorimetry, optical polarizing microscopy and X-ray diffraction measurements reveal liquid crystalline properties for all synthesized monomers and polymers. All three precursor olefinic monomers reveal cholesteric and smectic A phases. The olefinic monomer which contains two oligooxyethylene units in the spacer is the only one which reveals a twist grain boundary A phase and a blue phase, besides the cholesteric and smectic A phases. All three polysiloxanes present enantiotropic smectic A and chiral smectic C phases. The mesomorphic behaviours of the monomers and polymers are compared with those of the corresponding monomers and polymers without the lateral fluoro substituent. The results seem to demonstrate that incorporating a lateral fluoro substituent in the mesogenic cores of the monomers affects not only the mesophase thermal stability, but also the nature of the mesophases formed. However, incorporating a lateral fluoro substituent in the mesogenic cores of the polymers affects only the thermal stability of the mesophases formed. The lateral fluoro substituent has a more profound effect on the mesomorphic behaviour for the monomers than that for the polymers.