Novel liquid crystals and dopants (for induced ferroelectricity) possessing a chiral 2-oxetanone unit. A comparison with corresponding dioxolanones

The mesomorphic properties, induced spontaneous polarizations, and response times of a new type of liquid crystal and ferroelectric liquid crystal mixtures containing di- or trisubstituted 2-oxetanones as a chiral unit are described. By heating above 140°C oxetanones, bearing a three core mesogenic part, suffer cycloelimination of carbon dioxide yielding liquid-crystalline olefines with nematic, smectic C and higher ordered smectic phases, which are best suited as host materials for induced S_c* phases using the corresponding oxetanones as dopants. Compared with 1,3-dioxolan-4-ones recently synthesized and investigated, the oxetanones show minor mesomorphism.     

Synthesis and mesomorphic properties of chiral liquid crystals derived from (S)-2-(6-hydroxy-2-naphthyl)propionic acid with a methyleneoxy linking group

Three homologous series of chiral materials derived from (S)-2-(6-hydroxy-2-naphthly)propionic acid with a methyleneoxy linking group were synthesized for the investigation of mesomorphic properties. All the materials displayed enantiotropic SmA* and SmC* phases. The spontaneous polarization (P _s) and optical tilt angles in the SmC* phase of the chiral materials were measured. The maximum spontaneous polarizations are in the range 12.3-19.1 nC cm^-2. No significant difference could be found in the P _s values with respect to the various alkyl chiral chain lengths, n. The maximum optical tilt angles are in the range 25-30°. The optical tilt angles decrease with the increase in alkyl chain length, n.     

Frank Model and Spontaneous Emergence of Chirality in Closed Systems

In a closed system an irreversible enantioselective autocatalysis coupled to a mutual inhibition reaction, corresponding to a fast and low exergonic formation of the heterochiral dimer which reverts to the monomers in the final reaction work‐up, yields absolute asymmetric synthesis even in the absence of chiral polarizations. This is due to the very high chiral amplifications of the initial small statistical deviations from the ideal racemic composition. Moreover, this system is sensitive to very small chiral polarizations (energy differences between transition states below the mJ mol^?1 range). This behaviour can also be observed in reversible exergonic reactions, because the racemization time scale is substantially longer than that of the transformation of the initial reagents. The effect of the presence of other reactions likely to occur (i.e. non‐catalytic transformations, non‐enantioselective catalysis and homodimer formation) is discussed. Even if these decrease the sensitivity of the network in several chemical scenarios, the emergence of kinetically controlled spontaneous symmetry breaking is not hindered. These features, together with the response of the system to a sequential reaction procedure, suggest that a similar type of network is at the heart of the Soai reaction.     

Novel ferroelectric non-symmetric dimeric liquid crystals

The synthesis, characterization, mesomorphism and ferroelectric behaviour of ten new chiral dimeric compounds are reported. These compounds are non-symmetric dimers consisting of two mesogenic units joined by two different flexible spacers derived from S(-)-lactic acid. The mesogenic units contain ester and thioester groups. The effects of the length of the flexible spacer and the structure of the mesogenic units on the mesomorphism of the compounds are investigated. These compounds are ferroelectric and the spontaneous polarizations of some were measured, giving values of c. 10nC cm^-2.     

The effect of phase transitions on the response times of ferroelectric liquid crystal devices

The response times of ferroelectric liquid crystal devices are of great importance, and are known to be related to various physical properties of the chiral smectic C* phase, such as the spontaneous polarization, the cone angle and the rotational viscosity. We report measurements of the effect of the smectic phase transitions on the response times and show that these are influenced by the smectic C* to smectic A transition temperature.     

Novel ferroelectric liquid crystals and dopants for induced ferroelectric phases containing 3,4-epoxy-2-octanols as chiral unit

The synthesis of a new class of chiral smectic liquid crystals is described, along with transition temperatures, phase behaviour, spontaneous polarizations and related data. The general structure is shown in A. possessing a chiral unit derived from 3,4-epoxy-2-octanol. Two of these new compounds show seemingly antiferroelectric behaviour. The influence of the mesogenic core structure on mesophase behaviour and ferroelectric properties was investigated. The non-liquid crystalline representatives were examined as dopants for induced ferroelectric phases in an achiral matrix.     

New low molar mass organosiloxanes with unusual ferroelectric properties

A new low molar mass chiral organosiloxane mesogen and its racemic analogue have been synthesized and their mesomorphic and ferroelectric properties investigated. The chiral derivative, denoted A*B, exhibits one tilted enantiotropic ferroelectric smectic C mesophase over a broad temperature range, with very high tilt angles and moderate spontaneous polarization (36° and 19 nC cm^-2 at 20°C). The achiral siloxane derivative, denoted A*B, exhibits one broad enantiotropic smectic C phase. Preliminary electro-optic measurements indicate that the spontaneous polarization is weakly dependent on temperature between 10°C and 50°C, the latter being the S*_c to isotropic phase transition. The tilt angle and layer spacing are temperature independent, and current response times of less than 200 μs were measured at 25°C for fields of 10 V μ^-1. These results are discussed in comparison with those for side chain polymer liquid crystal structures and other low molar mass ferroelectric materials.     

A novel class of materials for ferroelectric liquid crystals containing siloxy chain end groups

Novel liquid crystals containing a siloxy chain as an end tail group instead of an alkyl chain were synthesized. The substitution effects were studied for ferroelectric liquid crystal materials. It was found that the temperature range for the chiral smectic C phase was reduced and shifted to lower temperature in comparison with the analogous alkyl chain derivatives. The crystallinity of the siloxy chain derivatives decreased and cholesteric phases were not observed. The influence of siloxy chains on ferroelectric liquid crystal properties, especially spontaneous polarizations and tilt angles, also greatly depended upon the mesogenic group structure. The X-ray diffraction results showed that the end tail group occupied a larger thickness in the chiral smectic C layer for the siloxy chain derivative than that for the alkyl chain derivative.     

Structure-property relationships of 'diluted' ferroelectric polysiloxanes

A series of new ferroelectric copolysiloxanes with systematically varied comonomer content ('dilution') has been synthesized. Good planar alignment could be achieved for all copolysiloxanes and they were studied with respect to their mesomorphic and ferroelectric properties. Broad enantiotropic S*_C phases and spontaneous polarizations up to 286 nC cm^-2 are found. X-ray diffraction experiments show a linear increase of the smectic layer spacing by 'dilution'. This points to a microphase separated structure of mesogenic groups and siloxane chains. It is found that the fixation of a mesogen to homopolysiloxane leads to an increase of P_s, whereas the 'dilution' of the mesogens with dimethylsiloxane units decreases P_s again. Based on the microphase separated model, it can be shown that the decrease of P_s is not only due to the decrease of the vol % of mesogenic groups. The coupling between different mesogens mediated by the polymer chain, has additionally to be taken into consideration. A remarkable drop in the response times τ with decreasing mesogen content is confirmed and switching times less than 1 ms were measured.     

Ferroelectric liquid crystals with fluoro- and aza-fluorenone cores: the effect of stereo-polar coupling

The chiral fluorenone mesogens (R)-1-fluoro-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)fluoren-9-one (2) and (R)-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)-3-azafluoren-9-one (3) were synthesized using a combined ortho-directed and remote metalation strategy, which also incorporates a Suzuki-Miyaura crosscoupling step. These compounds form chiral SmC* liquid crystal phases with reduced polarizations (P _o) of +475 and +332 nC cm^-2 at 10 K below the Curie point, respectively. These values are considerably larger than that previously reported for the unsubstituted fluorenone (R)-2-(2-octyloxy)-7-(4-undecyloxybenzoyloxy)fluoren-9-one (1), which is +111 nC cm^-2 at 10 K below the Curie point. Molecular modelling based on the Boulder model suggests that the larger polarizations result from a conformational bias of the fluorenone core dipole moment along the polar axis of the SmC* phase caused by stereo-polar coupling with the chiral 2-octyloxy side chain.     

Synthesis and SmC* properties of chiral liquid crystalline terephthalates

Chiral ester derivatives of terephthalic acid containing one, three, or five phenyl rings were prepared by using (S)-2-methylbutanol or (R)-2-chloropropanol as starting materials. The one-ring terephthalates did not exhibit any liquid crystalline phases, but one of them was used as a chiral dopant in ferroelectric mixtures. Elongation of the aromatic core structure to three and five phenyl rings stabilized the SmA phase, whereas a (monotropic) SmC* phase was detected in some three-ring and five-ring derivatives. In ferroelectric mixtures based on the terephthalates, spontaneous polarizations up to 340 nC cm2 were measured.     

Fast switching ferroelectric side-chain liquid-crystalline polymer and copolymer

New ferroelectric side-chain liquid-crystalline polymers, a copolymer and a homopolymer, with siloxane backbone and a triaromatic mesogen as the side group have been synthesized. The materials exhibit a chiral smectic C phase over a large temperature range extending to room temperature. They possess high values of spontaneous polarization: 105 nC cm^-2 for the homopolymer and 180 nC cm^-2 for the copolymer. The electro-optic switching time in the chiral smectic C phase is extremely fast (150 μs). In the smectic A phase, an electroclinic effect with switching times less than 100 μs and with field induced tilt angles of 18° is observed.     

Mesomorphic and ferroelectric properties of FLCP/FLC binary mixtures

We have prepared several ferroelectric polysiloxanes with two and three benzenic ring moieties. The siloxane backbone is favorable to ferroelectric S phase formation, and the chiral S phase is observed in all of the polymers. Some of the spontaneous polarizations are very high, more than 100 nC/cm² (10^?3 C/m²) and the response times are less than 1 ms near the I-S or S_a–SS transition. Several binary mixtures between FLC copoly-siloxanes and different low molar mass LC have been studied, and have shown the complete miscibility of these two components and richer mesomorphic sequences than for the polymers alone; for example, an N^*–S_a sequence.     

Spontaneous polarization and electro-optic behaviour of a ferroelectric liquid crystal cell fabricated with polyimide Langmuir-Blodgett films

The spontaneous polarization and electro-optic response of ferroelectric liquid crystals (FLCs) were investigated in a cell fabricated with a polyimide alignment layer coated by the Langmuir-Blodgett method. The surface properties of the cured polyimide layers were monitored by contact angle measurement, and by FTIR spectroscopy and AFM for the orientation and surface roughness, respectively. The apparent spontaneous polarization of an FLC determined in a practical sandwich-cell depended on various conditions such as cell thickness, cooling rate from the smectic A to chiral smectic C phase, and deposition pressure. Electro-optic response and decay times of FLCs were also measured. Furthermore, the ions in the FLC mixture reduced the magnitude of the effective electric field, but had no effect at high frequency.     

Synthesis and properties of optically active 1,3-diols and their derivatives as chiral dopants for ferroelectric liquid crystals

Abstract

New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1.     

Ferroelectric liquid crystals induced by dopants with axially chiral 2,2'-spirobiindan-1,1'-dione cores

The axially chiral dopants (R)-5,5'-, 5,6'-, and 6,6'-diheptyloxy-2,2'-spirobiindan-1,1'-dione ((R)-2, -3, and -4) were synthesized in optically pure form, and their absolute configurations were assigned by the exciton chirality method using circular dichroism spectroscopy. These new compounds were doped in four achiral liquid crystal hosts to give chiral smectic C* (SmC*) phases with spontaneous polarizations (Ps) that vary with the core structure of the host. The spontaneous polarization induced by the 5,5'-dialkoxy derivative (R)-2 is uniformly positive, whereas that induced by the 6,6'-dialkoxy derivative (R)-4 is uniformly negative and shows a different trend in host dependence. Polarization power (delta(p)) values range from +21 nC/cm2 for (R)-2 in 2',3'-difluoro-4-heptyl-4' '-nonyl-p-terphenyl (DFT) to -1037 nC/cm2 for (R)-4 in 4-(4'-heptyl[1,1'-biphen]-4-yl)-1-hexylcyclohexanecarbonitrile (NCB76). The unsymmetrical dopant (R)-3 behaves like a hybrid of the two symmetrical isomers, with lower absolute values of delta(p), on average, and varying signs of Ps. 2H NMR spectra of the doped mixtures using racemic mixtures of 2-4 with -OCD2C6H13 side-chains, in combination with phase diagrams, show that relatively minor changes in the dopant structure, that is, moving the alkoxy side-chains from the 5,5' to the 6,6' positions of the spirobiindandione core, have profound effects on dopant-host compatibility, and on the propensity of the dopant to exert chiral perturbations in the host environment. The variations in sign and magnitude of delta(p) as a function of alkoxy group positions are rationalized based on an analysis of zigzag conformations that conform to the binding site of the SmC host according to the Boulder model.     

Influence of fluorination extent on liquid crystalline properties of semi-perfluorinated phenylpyrimidine ferroelectric liquid crystals

A series of semi-perfluorinated ferroelectric liquid crystals, 2-[4-(2-fluoro-octyloxy)phenyl]- 5-(omega-n-perfluoroalkylalkyloxy)pyrimidines were prepared and their physical properties evaluated. All of the fluorinated phenylpyrimidines exhibited a chiral smectic C phase enantiotropically. The results showed that high fluorination extent favours the tilted chiral smectic C phase. Also, highly fluorinated compounds exhibited a large cone tilt angle and large spontaneous polarization. However, the response became slow as the fluorination extent increased. Although the compounds showed a large spontaneous polarization in the pure state, their spontaneous polarization power as chiral dopants was so small that very little spontaneous polarization could be measured.     

Synthesis and mesomorphic properties of fluoro-substituted chiral liquid crystals derived from (S)-lactic acid with alkoxyethanols

A homologous series of fluoro-substituted chiral liquid crystals derived from (S)-lactic acid and alkoxyethanols were prepared for investigation. Mesophases and their corresponding transition temperatures were identified by polarized optical microscopy and differential scanning calorimetry. The compounds exhibit a broad temperature range in the ferroelectric chiral smectic C (SmC*) phase; in particular, compounds with shorter alkyl chain lengths have an SmC* phase at ambient temperature. The physical properties of the ferroelectric SmC* phase, such as switching current, spontaneous polarization, optical tilt angle and electro-optical response, were also measured. The effects of fluoro substituent on the mesophases and physical properties of the chiral liquid crystals are discussed.     

Synthesis and ferroelectric properties of new chiral liquid crystals derived from (S)-lactic acid with alkoxyethanols

A homologous series of chiral materials derived from (S)-lactic acid with alkoxyethanols has been synthesized and their mesomorphic properties investigated. The mesophases and their corresponding transition temperatures were identified by differential scanning calorimetry and polarizing optical microscopy. The spontaneous polarization and electro-optical response of ferroelectric SmC* phase are measured and reported.     

Synthesis and properties of optically active 1,3-diols and their derivatives as chiral dopants for ferroelectric liquid crystals

New chiral dopants β-hydroxy ketones 1, 1,3-diols 2, 1,3-dioxanes 3 and 1,3-dioxan-2-ones 4 were designed and synthesized. Reaction of (R)-1,2-epoxyoctane with carbanions derived from 2-(4-substituted phenyl)-1,3-dithianes followed by hydrolysis of the resulting hydroxy dithianes afforded 1. Reduction of 1 gave the diols 2, which yielded 3 upon acetalization and 4 upon carbonation. The syn isomers of 2, 3, and 4 exhibited larger spontaneous polarizations, when applied as chiral dopants, than the anti isomers or hydroxy ketones 1.