Influence of the smectic A-nematic transitional order on the formation of the smectic phases of 4-n-hexyloxybenzylidene-4′-n-butyIaniline and 4-n-butyloxybenzylidene-4′-n-octyIaniline from an electrically deformed nematic phase

Abstract

The crucial role of the smectic A-nematic transitional order for the formation of the smectic A, B and G phases from an electrically deformed nematic phase of the liquid crystal 4-n-hexyloxy-benzylidene-4′-n-butylaniline (6O.4) with a typical smectic A-nematic first order transition and the formation of the smectic A and B phases from an electrically deformed nematic phase of the liquid crystal (4-n-butyloxy-benzylidene-4′-n-octylaniline (40.8) with a smectic A-nematic second order transition has been demonstrated. The nematic phase was deformed by an AC voltage of 2U,_th 5U _th and 10U _th, where U _th is the threshold voltage which causes the appearance of the Fréedericksz transition in the homeotropic nematic layer. The smectic textures have been observed on free cooling of the nematic phase or after the use of an oven. The smectic A phase of the liquid crystal 60.4 was observed with the formation of a clear smectic A-nematic phase boundary while the smectic A phase of the liquid crystal 40.8 has been formed from intermediate pretransitional stripes, observed by Cladis and Torza [1]. The homeotropic anchoring of the direction was crucial for the formation of the smectic phases of the liquid crystal 40.8 but not significant for the liquid crystal 60.4.     

The substituent effect on mesomorphic properties of 4-octyloxyphenyl 4-(4-R-3-nitrobenzoyloxy)benzoates and 4-(4-octyloxybenzoyloxy)phenyl 4-R-3-nitrobenzoates

Abstract

The thermal properties of 4-octyloxyphenyl 4-(4-R-3-nitrobenzoyloxy) benzo-ates (1) and 4-(4-octyloxybenzoyloxy)phenyl 4-R-3-nitrobenzoates (2) have been examined, where R = hydrogen, halogens, alkyl and alkoxy groups. The derivatives of compound 1 incorporating hydrogen, halogens, methoxy and nitro groups show a smectic A phase having a bilayer arrangement, and the others with a long alkoxy group show the S_A phase with the monolayer arrangement. The derivatives of compound 2 incorporating halogens, and the nitro group show the S_A phase with the monolayer arrangement. The alkoxy derivatives show a smectic C phase as well as the nematic phase. The nitro group at the lateral position tends to increase the ratio of the S_A-N transition temperature to the N-I. The effect of the nitro group on the smectic properties has been discussed in terms of the structural and electrostatic nature of the nitro group.     

Creation of nematic and reentrant nematic phases in bi- and multi-component smectic mixtures

Abstract

Experimental results referring to the transformation of smectic phases, mainly smectic A, into nematic and reentrant nematic phases are reviewed. A new explanation of some experimental results is proposed. Factors which are responsible for the depression of smectic phases in mixtures of polar mesogens are discussed and the possibility of forming mixtures with a broad temperature range of nematic phase from smectic compounds, which can be useful for liquid crystal displays (LCDs), is shown. A nematic gap observed in some cases between monolayer (S_A1) or monolayer and partially bilayer (S_Ad) smectics results from the differences in the organization of the molecules in the smectic layers. It is concluded that polar phase from smectic A₁ phases can be divided into two groups: (a) the first one is characteristic for compounds with the -NCS, -F, -CI, -I or ?COC _m H_{2m + 1} terminal group. The spacing of the smectic layer slowly expands with the increase in alkyl chain length and the structure of the smectic A₁ phase slowly changes to be more like the smectic A_d phase (d/1 > 1). It is proposed that such a smectic is called an enhanced monolayer smectic (S_A1e (b) the second one is typical for compounds with the -CN terminal group. This kind of smectic A₁ phase is rapidly transformed into the smectic A_d phase with increasing alkyl chain length. These latter monolayer mesogens easily form the reentrant nematic phase when they are mixed with other polar smectic mesogens.     

Ferroelectric liquid crystals induced by dopants with axially chiral 2,2′‐spirobiindan‐1,1′‐dione cores: diether vs. diester side‐chains

A series of axially chiral 5,5′‐ and 6,6′‐dialkanoyloxy‐2,2′‐spirobiindan‐1,1′‐dione dopants, (R)‐2 and (R)‐4a–4c were synthesized in optically pure form and their ferroelectric polarization powers, δ_p, measured in four liquid crystal hosts with isotropic (I)–nematic (N)–smectic A (SmA)–smectic C (SmC) phase sequences. The results show that the sign of polarization P _S induced by (R)‐2 and (R)‐4a–4c follows the same trend as that previously reported for the 5,5′‐ and 6,6′‐diheptyloxy‐2,2′‐spirobiindan‐1,1′‐dione dopants, (R)‐1 and (R)‐3. The polarization induced by (R)‐2 in the host DFT is below detection limits, and the sign of P _S was found to invert as a function of temperature at mole fractions as low as 0.01. On the other hand, the polarization power of the 6,6′‐diheptanoyloxy dopant (R)‐4b in the host NCB76 is ?1449 nC cm^?2, the fourth highest value reported so far, and more than three times the δ_p value of the 5,5′‐diheptanoyloxy analogue (R)‐2 in that host (+474 nC cm^?2). Results of ²H NMR experiments suggest that (R)‐4b exerts stronger local perturbations in NCB76 than (R)‐2, and that these perturbations may be chiral in nature.     

Optical activity and light scattering in the isotropic and smectic A* phases of a highly chiral smectic liquid crystal

Abstract

The results of optical activity measurements on the smectic A* phase of 1-methylheptyl 4′-[(4-n-tetradecyloxyphenyl)proprioloyloxy]biphenyl-4-carboxylate (14P1M7) and the chiral nematic phase of a chiral–racemic mixture of S-4-(2-methylbutyl)phenyl 4-decyloxybenzoate (CE6) are shown to be extremely similar. This is in full agreement with the proposed model of the A* phase as a twistgrain-boundary (TGB) phase. In addition, new light scattering measurements using circularly polarized light in a back-scattering geometry yield information on the fluctuations in the isotropic phase. Unlike in chiral nematics where only one structural mode is affected, the data show a strong deviation from the normal temperature dependence near the isotropic–smectic A* transition for two structural modes. Possible reasons for this behaviour in highly chiral smectic liquid crystals are discussed.     

Formation of periodic zigzag patterns in the twist-bend nematic liquid crystal phase by surface treatment

ABSTRACT

Zigzag patterns were successfully generated in the twist-bend nematic (N_TB) phase of 1-(4-cyanobiphenyl-4′-yl)-6-(4-cyanobiphenyl-4′-yloxy)hexane (CB6OCB) via simple surface treatment. A detailed microscopy study using polarised optical microscopy and fluorescence confocal polarising microscopy was performed to observe the director arrangement in the zigzags, where distinctive periodic patterns were found to be aligned perpendicular to the rubbing direction. These patterns originate from the structural instability and generation of splay deformation with focal conic domain-like structures that are typically found in smectic phases, revealing that the N_TB phase has physical properties similar to those of the smectic phase. Observation of these unusual zigzag patterns in the N_TB phase opens an avenue for use of this phase in potential applications such as optical modulators and gratings.     

Properties of new ferroelectric materials

A homologous series of chiral 4-(3-methylpentyl)benzenethio-4′-n-alkoxy-benzoates has been studied. These thioesters display a ferroelectric, chiral smectic C phase in addition to cholesteric and smectic A phases. A comparison is made between the thioester series and a phenylbenzoate, having the same molecular end group. The effect of the different central linkage on the transition temperature, and on the physical and ferroelectric liquid crystal (FLC) properties has been investigated. Several mixtures, containing these thioester components, were calculated and formulated to obtain room temperature chiral smectic C phases. Spontaneous polarization P_s values and electro-optical response times are correlated with chemical structures. Although these thioesters have very low P _s values, they are useful components for FLC mixtures because of their convenient chiral smectic C temperature ranges and their low viscosities.     

Azomesogens containing a β-chloroethyl terminal chain: synthesis and characterisation

In this paper, we present the synthesis and characterisation of two new mesogenic homologous series, β-chloroethyl 4-(4′-n-alkoxyphenylazo) benzoates (I) and the β-chloroethyl [4-(4′-n-alkoxybenzoyloxy)phenylazo]-4”-benzoates (II), containing a terminal β-chloro ethyl chain. Series I was synthesised by alkylation of β-chloroethyl 4-(4′-hydroxy phenylazo) benzoate with an appropriate alkyl halide, whereas series II was synthesised by esterification of β-chloroethyl 4-(4′-hydroxyphenylazo) benzoate with an appropriate 4-n-alkoxybenzoic acid. The molecular structures of these new compounds of both the series were characterised by combination of element analysis and a standard spectroscopic method. The mesomorphic behaviour was studied mainly by use of a polarised microscope and, in some cases, differential scanning calorimeter as well. In series I, all nine members synthesised exhibited only an enantiotropic smectic A mesophase. In series II, all 12 homologues exhibited an enantiotropic nematic mesophase; a smectic A phase appeared in the n-octyloxy derivative as an enantiotropic phase and persisted through to the n-hexadecyloxy member. The mesomorphic properties of both series were compared with each other and also with the properties of other structurally related series to evaluate the effects of the β-chloroethyl tail on mesomorphism.     

Detailed study of a two component smectic 4TPB–8OCB system with a nematic gap. Phase diagram and viscosity study

Abstract

The phase diagram of a two component system composed of two smectic compounds: 4-octyloxy-4′-cyanobiphenyl (8OCB) and 4-isothiocyanatophenyl 4-butylbenzoate (4TPB) was investigated. Three Miesowicz viscosity coefficients η₁, η₂, η₃ and the refractive indices at different temperatures as well as the enthalpies of the phase transitions were measured. It was stated, that the properties of the induced nematic phase, for example, the nematic phase existing between two smectic regions, are the same as the ones observed in the case of low viscosity nematic mesogens.     

Some Novel Smectic* Liquid-Crystalline Side-Chain Polymers

Abstract

Three acrylate side-chain polymers in which the mesogenic moieties are based on the 4-n-alkoxyphenyl-4′-(4″-methylhexyloxy) benzoates have been characterized by differential scanning calorimetry, optical microscopy and X-ray diffraction. For shorter flexible spacers (n = 2) both smectic A and C^* phases are observed thus making this polymer interesting for the fabrication of electro-optical devices based on ferroelectric properties (a smectic A phase is required for alignment purposes). For longer flexible spacers, (n = 6, 11) only the smectic A phase remains.     

V-shaped switching in binary mixtures of an achiral swallow-tailed material with the antiferroelectric liquid crystal (S)-MHPOBC

An achiral swallow-tailed material, 2-propylpentyl 4-(4′-decyloxybiphenyl-4-carbonyloxy)benzoate, p, showing SmA and SmC_alt phases was prepared for mixing (by weight percentage) with an antiferroelectric liquid crystal, (S)-MHPOBC, m, for the study. The binary mixture p/15/m85 using (S)-MHPOBC (85%) as a host doped with achiral material (15%) resulted in a phase sequence SmA-SmC*-SmC*_A. The electro-optic response of this mixture in the ferroelectric SmC* phase displayed V-shaped switching, while that in the antiferroelectric SmC*_A phase displayed a double hysteresis switching. The mixture p85/m15 possessed SmA* and SmC*_A phases; V-shaped switching was found in the antiferroelectric SmC*_A phase of this mixture. These optical phenomena implied that a binary mixture containing a larger amount of achiral swallow-tailed material and/or possessing relatively lower polarization favours the occurrence of V-shaped switching in the antiferroelectric phase. The results of this work also suggested that thresholdless V-shaped switching in chiral smectic liquid crystals can be achieved by mixing an achiral swallow-tailed material with an antiferroelectric liquid crystal.     

Liquid crystalline behaviour of hydrazide derivatives containing alkoxyazobenzene

Two series of dissymmetric hydrazide derivatives containing alkoxyazobenzene with nitro terminal group and octyloxy terminal group, N-4-alkoxyphenyl-N′-4-((4-nitrophenyl)azophenyl) benzohydrazide (Bn-NO₂, n indicates the number of carbon atoms) and N-4-octyloxyphenyl-N′-4-((4-octyloxyphenyl)azophenyl) benzohydrazide (B8-B8), were designed and synthesised, and their liquid crystalline properties were investigated by means of differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. It was found that B8-B8 with octyloxy terminal chains displayed monolayer smectic C phase, whereas Bn-NO₂ with nitro terminal group displayed SmA_d phase, and intermolecular hydrogen bonding was confirmed as the driving force. In addition, the effect of hydrogen bonding, dipole–dipole interactions and steric hindrance effect on the liquid crystalline structures were also discussed.     

The helical structure of highly ordered smectic phases

Optical studies of smectic phases have been performed in homogeneously oriented samples of chiral 4-(2′-methylbutyl) phenyl-4′-n-octylbiphenyl-4-carboxylate (CE8). The helix structure has been found in smectic phases C, I and J, but not in the smectic G phase. Two chiral phases have been found between S_I* and S_G phases. Up to now one of them has not been observed. The pitch of the helix has been measured in all of the twisted smectic phases, including the S_J* phase. The existence of the helix in this phase suggests that the correlations between smectic layers are not very strong.     

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract

The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)₂]_∞ 1 and [Cd(4, 4′-bipy)-(SCN)₂]_n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)Å; β = 115.54(2), V = 1465.8(8)ų, calculated density 1.530gcm^?3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (Å). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)Å; β = 109.71(3), V = 1381.8(4)ų calculated density 1.849gcm^?3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy to create two-dimensional planes.     

Simultaneous photoacoustic measurements of specific heat and thermal conductivity critical behaviour at a smectic A–nematic phase transition

Abstract

Simultaneous measurements of the thermal conductivity and specific heat at the smectic A-nematic phase transition in 4-n-octyl-4′-cyanobiphenyl (8CB) have been carried out with the photoacoustic technique. A critical increase in the thermal conductivity is reported. A critical decrease in the thermal diffusivity data confirms that the transition in 8CB is fluctuation dominated as also shown by the critical behaviour of the specific heat.     

Photocontrolled Phase Transitions and Reflection Behaviors of Smectic Liquid Crystals by a Chiral Azobenzene

The photocontrolled phase transitions and reflection behaviors of a smectic liquid crystal, 4‐octyl‐4′‐cyanobiphenyl (8CB), tuned by a chiral azobenzene, are systematically investigated. For the smectic 8CB doped with the chiral azobenzene (1R)‐(?)‐4‐n‐hexyl‐4′‐menthylazobenzene (ABE), the initial smectic phase can be switched to cholesteric and then to isotropic upon UV irradiation due to the trans‐to‐cis photoisomerization of ABE; however, no reflection band is observed. For the smectic 8CB doped with ABE and the chiral agent (S)‐(?)‐1,1′‐binaphthyl‐2,2′‐diol (BN), a reflection band located in the short‐wavelength infrared region is observed, which disappears after further UV irradiation. For the smectic 8CB doped with ABE and a chiral agent with higher helical twisting power, (S)‐2,2′‐methylendioxy‐1,1′‐binaphthalene (DBN), a phototunable system with cholesteric pitch short enough to reflect visible light is demonstrated. With a given concentration of the chiral dopant DBN, a reversible reflection color transition is realized tuned by the isomerization of azobenzene. The reverse phase transition from isotropic to cholesteric and then to smectic can be recovered upon visible irradiation. The photocontrolled phase transitions in smectic liquid crystals and the corresponding changes in reflection band switched by photoisomerization of azobenzene may provide impetus for their practical application in optical memories, displays, and switches.     

Azobenzene-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACT

The synthesis and characterisation of two new sets of non-symmetric liquid crystal dimers is reported, the 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yl)hexanes (CB6OABX) and 1-(4-substitutedazobenzene-4′-yloxy)-6-(4-cyanobiphenyl-4′-yloxy)pentanes (CBO5OABX). The terminal substituents are methyl, methoxy, butyl, butyloxy, nitrile and nitro. All the CB6OABX dimers exhibit twist-bend nematic (N_TB) and nematic (N) phases. The CBO5OABX dimers also all show an N phase but only the butyl and butyloxy homologues exhibit the N_TB phase. The transitional behaviour of the non-symmetric dimers is compared to that of the corresponding symmetric dimers, the 1,5-bis(4-substitutedazobenzene-4′-yloxy)pentanes (XABO5OABX) and either 1,7-bis(4-cyanobiphenyl-4′-yl)heptane or 1,5-bis(4-cyanobiphenyl-4′-yloxy)pentane. The XABO5OABX dimers all show a nematic phase and in addition, the butyl homologue exhibits a smectic A phase. The difference in transitional behaviour between the CB6OABX and CBO5OABX dimers is attributed to the difference in their molecular shapes arising from different bond angles between the para axis of the cyanobiphenyl unit and the first bond in the spacer. Specifically, the all-trans conformation of a CBO5OABX dimer is more linear than that of the corresponding CB6OABX dimer. Differences within each set of dimers are attributed to changes in the average molecular shape and the strength of the mixed mesogen interaction on varying the terminal group. Crystal structures are reported for CB6OABOMe, CBO5OABNO₂ and MeOABO5OABOMe.     

Liquid crystalline properties of dissymmetric molecules IV. The substituent effect on thermal properties of nematic and smectic A phases in three aromatic ring systems with ester linkages

This paper describes the effect of substituent and ester linkage on smectic properties for some derivatives of 4-R -phenyl 4-(4-octyloxybenzoyloxy)benzoates (1), 4-octyloxyphenyl 4-(4-R-benzyloxy)benzoates (2), 4-(4-octyloxybenzoyloxy)phenyl 4- R -benzoates (3), and 4-R-phenyl 4-octyloxyphenyl terephthalates (4) where R = OCH₃, CH₃, OC₈H₁₇, C8H17, halogens, CF₃, OCF₃, CN, NO2, etc. The thermal properties are discussed in terms of the electrostatic nature of the substituents and the relative orientation of the ester groups with respect to both terminal substituents. The substituent effect on the layer structure of the smectic A phase is also examined by means of a small angle X-ray analysis.     

N.M.R. study of collective molecular motions in smectogen liquid crystals

Abstract

The proton spin relaxation dispersion, T ₁(v), was studied by field-cycling techniques over a broad Larmor frequency range in the nematic and smectic phases of several liquid crystals (4,4′-bis-heptyloxyazoxybenzene, 4-cyano-4′-8-alkylbiphenyl, 4-cyano-4′-9-alkylbiphenyl, 4-cyano-4′-11-alkylbiphenyl and 4-cyano-4′-9-alkoxybiphenyl) with different sites of the nitrogen atom. The results can be explained quantitatively in terms of nematic and smectic order fluctuations (T ₁ ∝ v ^1/2, T ₁ ∝ v ¹), molecular self-diffusion, molecular rotations and up to six cross-relaxation resonances due to a nitrogen-proton coupling The order fluctuations contribution and the transition from the v ^1/2 to the v ¹ dispersion profile occurs always at Larmor frequencies in the kilohertz range. Some additional measurements of the frequency dependence of the dipolar relaxation time T _1D(v), are not in accord with existing theories.     

Phase-transition studies of 5O.5 and 9O.4

As part of our detailed comparative studies of groups of liquid-crystalline compounds that belong to a homologous series, we present phase-transition studies of the compounds N-(4-n-pentyloxybenzylidene)4′-n-pentylaniline (5O.5) and N-(4-n-nonyloxybenzylidene)4′-n-butylaniline (9O.4) using different experimental techniques. The compound 5O.5 is reported to exhibit a phase sequence N, S_A, S_C, S_B and S_G, while 90.4 shows the sequence S_A, S_F and S_G. The salient features of our work on 5O.5 are (i) a new smectic F phase is found in place of the reported smectic B phase, which is confirmed by both miscibility and X-ray studies; (ii) the formation of smectic-C-like short-range order in the nematic phase well above the S_A-N transition; and (iii) a large tilt-angle variation in the smectic C phase (0–23·5°C) in a small temperature range (4·1°C). The phase changes across the S_A-I transition, and for the first time across S_F-S_A transition, are carried out by volumetric studies. The detailed inferences of these are also presented.