Orientational ordering in some nematogens deviating from the classical rod-shape

Several new laterally substituted liquid crystalline compounds have been synthesized. They have the same main core which contains four rings (two aromatic, two alicyclic) with two lateral substituents introduced on the same side of one of the inner rings. One of the substituents is a 4-X-benzyloxy group (X=CH3,CN,Cl) and the other is a hexyloxy chain. The presence of the lateral aromatic substituent makes these compounds deviate markedly from the classical rod-shape. However, a wide enantiotropic nematic phase is present for all the compounds. The order parameters of the chain and the para -disubstituted aromatic rings were obtained by using a 2D 13C NMR technique with variable angle spinning. The temperature dependence of the order parameters was estimated using 13C chemical shifts with slow spinning of the sample parallel to the magnetic field. The results indicate that the two lateral substituents are more or less folded back along the mesogenic core. Thus, the flexible lateral chain is found to be roughly aligned with the molecular long axis, whereas the para axis of the less flexible aromatic branch makes a considerable angle with the molecular long axis imposed by the core, substantially increasing the mean width of the molecule. The core ordering does not seem to be influenced by the type and position of the substituents. The folding back of the lateral chain and the substantial tilt of the lateral aromatic branch with respect to the core main axis are confirmed by the X-ray structure of a parent compound.     

The effect of a lateral aromatic branch on the orientational ordering of laterally alkoxy substituted nematics

Two new mesogenic series have been synthesized. They have the same main core which contains four aromatic rings, with two lateral substituents on the same side of one of the inner rings. One of the substituents is a 4-chlorobenzyloxy group and the second is an alkoxy chain. The positions of the lateral substituents are different in the two series. Despite the large aromatic branch, an enantiotropic nematic phase is obtained for most of the compounds. The orientational ordering behaviour of these new compounds has been investigated by C-13 NMR, and two isomeric compounds containing a lateral dodecyloxy chain were chosen for the study. The order parameters of the chain were obtained by a 2D C-13 NMR technique with variable angle spinning. The temperature dependence of the order parameters was determined using the C-13 chemical shifts with slow spinning of the sample parallel to the magnetic field. The first methylene fragment in each lateral substituent of each compound has a positive C-H bond order parameter, implying that this fragment adopts a cis conformation in the nematic phase. The two lateral substituents are folded back along the mesogenic core in opposite directions. The lateral chain is found to be roughly aligned along the molecular long axis imposed by the core, whereas the para -axis of the phenyl ring in the lateral aromatic branch makes a considerable angle with the molecular long axis. It was also found that the different patterns of substitution do not affect the position of the molecular long axis to any large extent.     

Laterally dibenzyloxy-branched nematogens with large nematic range and rich solid polymorphism

Mesogenic compounds containing four rings in the core usually have very high melting points. However, when two identical lateral benzyloxy groups are introduced on the same side of one of the central rings, the melting point is lowered dramatically and a large nematic range is retained. This range is affected by the bulkiness of the para-substituents in the lateral rings. Methyl groups can be introduced in the ortho- or meta-positions with a consequent decrease in the melting temperature without much affecting the nematic range. These compounds exhibit a rich solid polymorphism which is certainly related to the effect of the conformations of the lateral substituent on the molecular arrangment in the solid phase. Some preliminary NMR experiments on the nematic phase indicate that the molecular long axis coincides with the core axis, whereas the para-axis of the lateral fragment makes an angle close to the magic angle with respect to the molecular long axis.     

Laterally dibenzyloxy-branched nematogens with large nematic range and rich solid polymorphism

Mesogenic compounds containing four rings in the core usually have very high melting points. However, when two identical lateral benzyloxy groups are introduced on the same side of one of the central rings, the melting point is lowered dramatically and a large nematic range is retained. This range is affected by the bulkiness of the para-substituents in the lateral rings. Methyl groups can be introduced in the ortho- or meta-positions with a consequent decrease in the melting temperature without much affecting the nematic range. These compounds exhibit a rich solid polymorphism which is certainly related to the effect of the conformations of the lateral substituent on the molecular arrangment in the solid phase. Some preliminary NMR experiments on the nematic phase indicate that the molecular long axis coincides with the core axis, whereas the para-axis of the lateral fragment makes an angle close to the magic angle with respect to the molecular long axis.     

Nematogens with more flexible chains than aromatic rings in the core

Mesogens containing four rings in the main core can accommodate one terminal and two nearby lateral chains on each outside aromatic ring. These compounds containing six chains present an enantiotropic nematic range which is influenced by the rigidity of the links. The conformational behaviour of the first methyleneoxy group within the chains was investigated by one and two dimensional 13C NMR. The sign of the jump in chemical shifts when entering the nematic phase indicates the folding of each lateral branch. Dipolar oscillations during cross-polarization contact provide the values of the bond order parameter. The two first lateral fragments do not behave in the same way, demonstrating the influence of the fragment along which the chain is back folded.     

Order parameters of the mesogenic core in two nematic liquid crystals containing a four-unit link

A series of compounds containing a four-unit link, 4'-n-alkylphenyl-4-n-hexyloxycinnamates, has been synthesized, and their mesomorphic behaviour has been determined. The orientational ordering of two compounds in this series has been studied in detail by 2D carbon-13 nuclear magnetic resonance with variable angle sample spinning. The carbon-proton dipolar coupling constants were obtained and the order parameters were calculated for different molecular segments (two phenyl rings, the central link containing an ethylenic motif, and the methylene carbons of the alkoxy chain). The temperature dependence of the local order parameters of each fragment were determined using these data and C-13 chemical shifts which were measured as a function of temperature. In these non-rigid molecules, the ratio between the order parameters of the two phenyl rings was found to be temperature dependent. The ring bearing the double bond is more ordered at low temperatures compared to the ring bearing the short alkyl chain, but this behaviour is reversed near the clearing point. The position of the major axis of the rigid core was calculated from the order parameter of one ring and the order parameter of the ethylenic link. It was found that this major axis forms a constant angle with respect to the para axis of the phenyl ring connected to the ethylenic group. On the other hand, the angle of this major axis with respect to the para axis of the phenyl ring connected to the carboxylic group is temperature dependent, varying from 11° at T/T_NI = 0·92 to 7° at T/T_NI = 0·98.     

Development of Donor-π-Acceptor-Type Fluorinated Tolanes as Compact Condensed Phase Luminophores and Applications in Photoluminescent Liquid-Crystalline Molecules

Fluorinated tolanes, produced by introducing fluorine atoms into one of the aromatic rings of tolane, emitted almost no fluorescence in a solution state, but the fluorescence intensity increased dramatically in the crystalline state because of intermolecular H⋅⋅⋅F hydrogen bonds. The photoluminescent (PL) colors depend on the molecular orbitals, dipole moments, and molecular aggregated structures can be varied by controlling terminal substituents along the major molecular axis. The introduction of a long alkoxy or semifluoroalkoxy unit as a flexible chain into the terminal positions along the major molecular axis induced the formation of a liquid-crystalline (LC) phase; fluorinated tolanes act both as luminophores and as mesogens, leading to the molecular design of new photoluminescent LC molecules (PLLCs). The results also indicated that a fluorinated tolane dimer, which consists of two fluorinated tolanes linked by a flexible alkylene spacer, also becomes a novel PLLC.     

Orientational ordering of ferroelectric thiobenzoate liquid crystals

The orientational ordering of a series of ferroelectric thiobenzoate liquid crystals was studied by natural abundance ¹³C NMR spectroscopy. The technique used was a combination of variable angle spinning (VAS) and separated local field spectroscopy (SLF). With rapid sample spinning about an axis forming an angle of c. 45° with respect to the magnetic field, the smectic director aligns parallel to the spinning axis, leading to narrow peaks in the ¹³C NMR spectrum. The two-dimensional NMR spectroscopic method SLF allows the observation of decoupled ¹³C signals in the ω2 dimension and first-order Csbnd;H splitting patterns in the ω1 dimension, from which the dipolar C-H coupling constants for individual bonds can be obtained. The order parameters for different molecular segments of eight different compounds, all containing two phenyl rings linked by a thioester group, were obtained this way. A considerable influence of length, branching and chirality of the aliphatic chain on the order parameters was observed.     

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.     

New laterally aromatic branched liquid crystal materials with large nematic ranges

Abstract

Three new homologous series of mesogens containing three rings in the main structure and a lateral aromatic branch have been synthesized. When the lateral aromatic branch is attached to the middle ring, monotropic phases are observed, and there is a strong tendency to form the smectic C phase. When the lateral aromatic branch is attached to an outer ring, the compounds possess purely enantiotropic nematic phases. The terminal alkoxy chain in the outer ring which has a lateral aromatic substituent can be replaced by a rigid group without disturbing the large nematic range. Selective introduction of a particular substitutent may be useful for the construction of devices possessing desirable characteristics such as non-linear optical properties.     

Effect of the chain length on the thermal and analytical properties of laterally biforked nematogens

Three laterally substituted liquid crystals were synthesized in order to investigate the effect of a lateral biforked chain on the thermal and analytical properties. The mesogenic molecules have the same core containing four aromatic rings connected by two ester and one diazo linkages, they differ by the length of one chain within the lateral biforked substituent. The phase transition temperatures were obtained by polarized light microscopy and differential scanning calorimetry (DSC). The clearing temperature and the nematic range decrease with increasing length of the lateral biforked chain. The stationary phases derived from these nematogens provide excellent resolution of various classes of compounds, including aromatic hydrocarbons (AH), substituted benzenes, polycyclic aromatic hydrocarbons (PAH), phenols and volatile organic compounds (VOC) present in the essential oils. The selectivities of the stationary phases were found to decrease according to the length of the side chain.     

Synthesis and mesomorphic properties of four ring,rod-like fluorene derivatives – the influence of the lateral substitution on mesomorphic properties of 2,7-bis(4-alkylphenyl)-fluorenes

ABSTRACT

This work presents new rod-like compounds being fluorene derivatives linked with other parts of the core at 2 and 7 positions – its synthesis and properties. The fluorene moiety is located in the central position of the four rings molecular core. The chain system in most cases was symmetrical and limited to pentyl or hexyl chains. To study the influence of the lateral substituents on mesomorphic properties two types of substituents have been incorporated, centrally located various short alkyl groups at fluorene’s 9,9 positions and outer core fluorosubstitutions located at side phenyl rings. All synthesised compounds exhibit liquid crystalline properties, where for laterally non-substituted and fluorosubstituted derivatives the dominant phases are smectics, while the nematics phases (nematic and chiral nematic – observed mostly on cooling cycle) occurs for compounds having alkyl substituents at 9,9 positions of fluorene. The synthetic methodology and mesomorphic properties of title compounds will be presented in detail as well as photophysical properties such as UV-visible absorption spectra and fluorescence spectra.     

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.     

Structure and substitution effects on the thermotropicity of some polyesters and model compounds

Abstract

The variations which occur in the thermal stability of the nematic mesophase as a function of the structure of the mesogenic moiety are considered here for the role played by three types of modifications. These are changes in the chemical nature of the mesogenic group, variation of the axial ratio of the rigid core and the presence of lateral substituents on the aromatic rings. Low molecular weight and polymeric liquid crystals of similar chemical nature have been investigated in order to see if parallel structure—property relationships exist between the two groups of compounds. In particular, starting from a mesogenic group built up of three aromatic rings connected by ester bonds, we have introduced the following modifications: (i) substitution of the central —COOC₆H₄OOC—with the—CH[dbnd]N—N[dbnd]CH— group; (ii) addition of two oxybenzoic end units to increase the length of the mesogenic moiety; (iii) introduction of two or more lateral methoxy substituents on the aromatic rings. The compounds were obtained by low temperature solution esterification between acyl chlorides and phenolic derivatives in the presence of a tertiary amine. Syntheses generally took place through the preliminary preparation of suitable intermediates. The thermal stability and the nature of the mesophases have been examined by different techniques. An interpretation of the results on the basis of the axial ratio and the strength of orientation dependent mutual attractions is attempted for model compounds. As far as polymers are concerned thermodynamic parameters follow the expected trend, if compared with those of low molecular weight analogues. Qualitatively models and polymers exhibit a similar dependence of mesophase stability on geometrical and electronic effects.     

Structure and substitution effects on the thermotropicity of some polyesters and model compounds

The variations which occur in the thermal stability of the nematic mesophase as a function of the structure of the mesogenic moiety are considered here for the role played by three types of modifications. These are changes in the chemical nature of the mesogenic group, variation of the axial ratio of the rigid core and the presence of lateral substituents on the aromatic rings. Low molecular weight and polymeric liquid crystals of similar chemical nature have been investigated in order to see if parallel structure—property relationships exist between the two groups of compounds. In particular, starting from a mesogenic group built up of three aromatic rings connected by ester bonds, we have introduced the following modifications: (i) substitution of the central —COOC₆H₄OOC—with the—CH=N—N=CH— group; (ii) addition of two oxybenzoic end units to increase the length of the mesogenic moiety; (iii) introduction of two or more lateral methoxy substituents on the aromatic rings. The compounds were obtained by low temperature solution esterification between acyl chlorides and phenolic derivatives in the presence of a tertiary amine. Syntheses generally took place through the preliminary preparation of suitable intermediates. The thermal stability and the nature of the mesophases have been examined by different techniques. An interpretation of the results on the basis of the axial ratio and the strength of orientation dependent mutual attractions is attempted for model compounds. As far as polymers are concerned thermodynamic parameters follow the expected trend, if compared with those of low molecular weight analogues. Qualitatively models and polymers exhibit a similar dependence of mesophase stability on geometrical and electronic effects.     

Terminal end‐group efficiency for the nematic phase using model bicyclo[2.2.2]octanes

The synthesis is reported of new liquid crystals incorporating the 1,4‐disubstituted bicyclo[2.2.2]octane ring and a series of substituents in a terminal position on the molecular core. The nature of the terminal substituent is varied from apolar with a small dipole moment to polar with a strong dipole moment. The angle of the dipole moment with respect to the molecular axis is also varied. An updated order of terminal group efficiency for substituents in a terminal position for the nematic phase is provided. The bicyclo[2.2.2]octane ring shields halogen substituents in a lateral position on phenyl rings attached to the bicyclooctane ring to a small degree and reduces the steric efects of these substituents, giving rise to high relative nematic–isotropic transition temperatures.     

Terminal end-group efficiency for the nematic phase using model bicyclo[2.2.2]octanes

The synthesis is reported of new liquid crystals incorporating the 1,4-disubstituted bicyclo[2.2.2]octane ring and a series of substituents in a terminal position on the molecular core. The nature of the terminal substituent is varied from apolar with a small dipole moment to polar with a strong dipole moment. The angle of the dipole moment with respect to the molecular axis is also varied. An updated order of terminal group efficiency for substituents in a terminal position for the nematic phase is provided. The bicyclo[2.2.2]octane ring shields halogen substituents in a lateral position on phenyl rings attached to the bicyclooctane ring to a small degree and reduces the steric efects of these substituents, giving rise to high relative nematic-isotropic transition temperatures.     

Substituent effects on aromatic stacking interactions

Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl(3), and by comparison with the solid state structures of model compounds. The structural similarity of the complexes makes it possible to apply the double mutant cycle method to evaluate the magnitudes of 24 different aromatic stacking interactions. The major trends in the interaction energy can be rationalised using a simple model based on electrostatic interactions between the pi-faces of the two aromatic rings. However, electrostatic interactions between the substituents of one ring and the pi-face of the other make an additional contribution, due to the slight offset in the stacking geometry. This property makes aromatic stacking interactions particularly sensitive to changes in orientation as well as the nature and location of substituents.     

Monte Carlo simulations of a liquid crystal copolymer in the solid state

The condensed phase of the alternating copolyester of p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) is investigated by studying the room temperature packing arrangement of the copolymer chains. A molecular modeling methodology is employed with a Monte Carlo sampling of the configurational phase space. Realistic poly(HBA-alt-HNA) polymer chains are represented by an explicit atom representation of the HBA/HNA dimers. States are sampled from the NVT ensemble using a sampling scheme consisting of (1) valence and torsional variations, (2) rigid body rotations of the chain about the chain axis, and (3) rigid body translations of the chain. The effect of chain packing on the conformation of chains, as well as the relative intra- and intermolecular orientations of aromatic rings, is investigated. Correlation of chain positioning along the chain axis is dominated by aromatic rings maintaining a center-to-center plane of registry. These layers of aromatic units pack with a preference for edge-to-face orientations in a herringbone-type pattern and have an intermolecular ring angle between the pairs of aromatic rings in the unit cell that is ca. 68°. The aromatic rings, on average, are rotated 38° out from the b–c plane. The phenylene rings of these copolyesters are less restricted in their relative orientation in comparison to the naphthalene rings. Intramolecular orientational probability density distributions indicate a preference for staggering the successive aromatic rings along the chain, with a staggering angle of ca. 66°. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 727–741, 1998     

Synthesis and characterization of thiophene-containing liquid crystals

Six series of liquid crystal materials containing a 2,5-disubstituted thiophene unit were synthesized. The liquid crystal compounds obtained were characterized by NMR, differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction techniques. The properties of liquid crystalline phases were investigated as a function of spacer units, number of aromatic core rings and different terminal moieties. Cyano, methoxy and iodo groups were used as terminal groups. It is found that: (i) compounds having one thiophene ring and one phenyl ring connected by an ester group, with a length/breadth value of 2.1, exhibit no mesophase, while other compounds containing two biphenyl rings, with a length/breadth ratio of 2.7, show mesophases; (ii) the polarity of terminal groups and the flexible spacer length significantly affect the thermal behaviour of these compounds; (iii) the nematic transition range of cyano-containing compounds decreases with increasing length of the flexible spacer, and long alkenyloxy chains tend to facilitate the formation of the smectic phase and suppress the nematic phase in all the mesogenic compounds synthesized.