Liquid crystal dimers possessing chiral rod-like anisometric segments: synthesis, characterization and electro-optic behaviour

Several new optically active liquid crystal dimers comprising pro-mesogenic cholesterol and a chiral diphenylacetylene (tolane) segment, covalently linked in an end-to-end fashion through a flexible spacer, have been synthesized and investigated for their mesomorphic behaviour with the aid of optical, calorimetric and X-ray diffraction studies. Five unsymmetrical dimers, designed on the basis of recent work, involve molecular structural variations of the tolane mesogenic entity with a view to stabilizing a wide thermal range smectic A (SmA) phase featuring the electroclinic effect. Three different chiral chains, namely, (S)-1-methylheptyloxy, (S)-2-methylbutyloxy, (3S)-3,7-dimethyloctyloxy, with or without polar (nitro or fluoro) lateral substituents, were incorporated, while keeping the length (C₆) of the spacer constant. As expected, all the dimers exhibited a SmA phase. A few also showed chiral nematic (N*) and/or twist grain boundary and/or chiral smectic C (SmC*) phases. Remarkably, some of these oligomesogens, upon melting, had a stable SmA phase over a wide thermal interval (100-150°C); this state seems to be stable for a long period of time. Electro-optic studies, including optical tilt angle as well as temporal response as a function of temperature, were carried out in the SmA phase. The SmC* phase was also investigated for its electrical switching and optical tilt angle, as well as spontaneous polarization as a function of temperature. These studies showed that the mesophase response to an applied field is weak and is independent of variations in the dimer investigated.     

Mesomorphic chiral non-symmetrical dimers: synthesis and characterization

The preparation and phase transitional properties of several optically active non-symmetrical dimers are reported. Two types of dimeric mesogens formed by covalently combining pro-mesogenic cholesterol with either phenyl 4-cyanobenzoate (polar) or phenyl trans-4-pentylcyclohexanecarboxylate (apolar) cores in an end-to-end fashion through an ω-oxyalkanoyl spacer were investigated. The phase behaviour of these two types of dimers differs, indicating that the nature and extent of mesomorphism are sensitive to the structure of the mesogen attached to the cholesterol. However, within the series, the spacer parity greatly influences the clearing temperatures of the materials, as expected. In general, all the compounds display an enantiotropic chiral nematic (N*) phase; several of them also stabilize smectic and/or twist grain boundary phases. The optical properties of the N* phase of all the compounds were investigated with the aid of both UV-visible and chiroptical spectroscopic techniques. These complementary studies revealed that the dimers exhibit an odd-even effect in the wavelength of selective reflection, with even-parity members having higher values, similar to previous reports. The chiroptical spectroscopy indicated that the N* pitch is right-handed for all the investigated dimers, which is in accordance with the fact that most steroidal esters are right-handed.     

Oxadiazole-based unsymmetrical chiral liquid crystal dimers: synthesis and mesomorphic properties

The synthesis and liquid crystalline properties of novel chiral Schiff's base dimers containing the 1,3,4-oxadiazole ring are reported. The length of the terminal S-alkyl chain has been varied. All the compounds synthesised were thermally stable and exhibited enantiotropic mesomorphism, showing either SmC*–SmA–TGB–N*–BP or SmC*–SmA phase sequence.     

Facile synthesis of new oxalate dimers of naturally occurring 3-hydroxysteroids

Several symmetrical steroidal oxalate dimers were synthesised from naturally occurring 3-hydroxysteroids, namely, estrone (1), DHEA (3), pregnenolone (5), cholesterol (7), 5D-cholestane (9), and stigmasterol (11), using oxalyl chloride. Full spectroscopic data for all the new compounds are presented. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 442–444, September–October, 2006.     

Liquid crystals derived from 2-phenylisoindoles: synthesis and characterization

2-Phenylisoindole was investigated as the rigid core unit in a series of asymmetric mesogenic molecules. When the 2-phenylisoindole core was terminated with a hexyl tail, no mesophase formation could be observed. When 4- n -(tridecafluorohexyl) was used, however, both monotropic and enantiotropic phase behaviour were observed. It was found that most functionalities at the anhydride 5-position results in the formation of smectic A (SmA) phases in the temperature range 70-180°C. Functionalities at the anhydride 4-position suppress mesophase formation. Large substituents (-Br, -NO2) and symmetric substitution patterns (5,6-dichloro, 4,7-dichloro and 4,5,6,7-tetrachloro) on the anhydride moiety increase the melting point and destabilize the mesophase. Temperature dependent X-ray diffraction experiments suggest an interdigitated SmA packing for this family of compounds.     

Synthesis and mesomorphic properties of chiral liquid crystal dimers derived from azobenzene and substituted naphthol

Symmetrical liquid crystal dimers bis{2-alkyl-(S)-(+)-2-(6-[4-4′-decyloxyphenylazo)-benzoyloxy]-2-naphthyl)propinate} have conveniently been designed, synthesised and their mesomorphic properties were investigated. These dimers possess two identical mesogenic units with each of them attached to the terminal end of a flexible spacer (–C _n H_2n ; where n = 6–10). The respective mesogenic unit was made up from a naphthyl ring attached to the alkyloxylated azobenzene via the ester (COO–) bond. The chiral moiety attached to the 6-position of the naphthyl ring possesses a terminal carboxylic group COO– which linked up the mesogenic unit and the spacer. The thermal and optical properties for the ultimate compounds at different temperature were studied explicitly with the aids of differential scanning calorimetry and polarising optical microscopy. All dimers exhibit unambiguously the monotropic nematic and smectic A phases. The homeotropic alignment of the molecules within the anisotropic region was further confirmed through the application of homogeneously treated cell.     

Total synthesis of naturally occurring chiral cyclopropane fatty acids and related compounds

Cyclopropane fatty acids (CFAs) and related compounds containing CFAs commonly occur in various natural sources, including plants or microorganisms. Some CFAs exhibit intriguing biological activities such as antifungal or immunosuppressive activities. Due to their biological importance and structural features, a number of synthetic studies have been conducted to date. These total syntheses have helped to elucidate their structural determinants or biological activities. Herein the total syntheses of naturally occurring CFAs and related compounds are summarized.     

Liquid crystal dimers and oligomers

A liquid crystal dimer is composed of molecules containing two mesogenic groups linked via a flexible spacer. Initial interest in these materials stemmed from their ability to act as model compounds for semi-flexible main chain liquid crystal polymers but are now of fundamental interest in their own right because their behaviour is significantly different to that of conventional low molar mass liquid crystals. Recently research has begun to focus also on higher monodisperse oligomers such as trimers and tetramers consisting of molecules containing either three or four mesogenic units, respectively, linked via flexible spacers. In this review the most recent developments in our understanding of structure–property relationships in liquid crystal dimers and higher oligomers is discussed.     

Convenient methods for the synthesis of highly functionalized and naturally occurring chiral allenes

A convenient two step procedure to access highly functionalized chiral allenes using chiral N-methylcamphanyl piperazine derivatives is described. In this transformation, chiral propargylamines are obtained in 79–96% yields with up to 99:1 dr by the CuBr catalyzed reactions of chiral piperazine derivatives with 1-alkynes and aldehydes containing functional groups, which are converted into chiral allenes in the presence of zinc bromide, affording the chiral allenes in 59–85% yields and with up to 99% ee. The antifungal agent Sapium japonicum and an allene precursor intermediate for the synthesis of the pheromone of the male dried bean beetle 15 are obtained in 72–78% yields and with up to 98% ee following this methodology.     

Liquid crystal oligomers: going beyond dimers

This review focuses on structure-property relationships in liquid crystal oligomers, which consist of molecules containing two or more mesogenic units linked via flexible spacers essentially in a linear fashion and so does not consider, for example, liquid crystal dendrimers and tetrapodes. Previous reviews have tended to focus mainly on liquid crystal dimers in which just two mesogenic units are interconnected by a single spacer. By contrast, this review is largely devoted to higher oligomers such as liquid crystal trimers and tetramers containing three or four mesogenic units connected by two or three spacers, respectively.     

Grafted self-assembled monolayers derived from naturally occurring phenolic lipids

Self-assembled monolayers grafted onto silicon surfaces were obtained from the hydrosilylation products by trialcoxysilanes of naturally occurring phenolic lipid allyl ethers. The as-obtained materials were characterized by various physical and physicochemical methods. Thus, contact angles of water drops showed that they possess very high hydrophobicity. Their excellent regularity was corroborated by AFM microscopy. The frequencies of the stretching CH2 infrared modes indicate the presence of alkyl chains mainly in the trans/trans conformation. Additionally, optical ellipsometry and quartz microbalance measurements enabled us to estimate the thickness of the films. The results, as a whole, are in good agreement with the formation of densely packed monolayers.     

Microwave-assisted synthesis,characterization, and antimicrobial activity of some odorant Schiff bases derived from naturally occurring carbonyl compounds and anthranilic acid

Nine odorant Schiff bases, namely 2-(4-methoxybenzylideneamino) benzoic acid, 2-(benzylideneamino) benzoic acid, 2-(3-phenylallylidene amino) benzoic acid, 2-(3,7-dimethyloct-2,6-enylideneamino) benzoic acid, 2-(3,7-dimethyloct-6-enylideneamino) benzoic acid, 2-(4-isopropylbenzylideneamino)benzoic acid, 2-(3,4-dimethoxybenzylideneamino) benzoic acid, 2-(1-phenylethylideneamino) benzoic acid, and 2-[(4-(2,6,6-trimethylcyclohex-2-enyl)-but-2-enylideneamino)benzoic acid, were prepared by condensation of anthranilic acid with corresponding naturally occurring carbonyl compounds (anisaldehyde, benzaldehyde, cinnamaldehyde, citral, citronellal, cuminaldehyde, veratraldehyde, acetophenone, and α-ionone) employing conventional and microwave irradiation methods. These compounds were characterized with the aid of elemental and spectral (FT-IR, ¹H NMR, and ¹³C NMR) analysis. Microwave irradiation method was efficient in terms of reduced reaction time, solvent use, and increased yields of these compounds without affecting their olfactory characteristics. These Schiff bases also exhibited olfactory characteristics for various fragrance compositions and varied antimicrobial activity against Aspergillus niger, Penicillium chrysogenum, Staphylococcus aureus, and Escherichia coli.     

Synthesis and characterization of novel chiral dimers exhibiting highly frustrated liquid crystal phases

Two novel series of optically active dimers comprising cholesterol and biphenyl-4-yl 4-(n-alkoxy)benzoate cores interlinked though either an odd-parity/even-parity spacer have been prepared and characterized. They stabilize an extremely complex, frustrated liquid crystalline state viz., the twist grain boundary (TGB) phase with chiral smectic C structure, denoted as TGBC^∗ phase, over a wide (50–110 °C) temperature range. Notably, the dimers with an odd-parity spacer show an additional frustrated liquid crystal phase namely, the blue phase (BP). The presence of such frustrated phases suggests that the synthesized dimers are characterized by high enantiomeric excess and strong molecular chirality. Thus, 12 new optically active, nonsymmetric dimers reported herein constitute new examples of rarely found strongly chiral, optically pure dimers showing frustrated liquid crystal phase over an adequately wide thermal range.     

Supramolecular non-symmetric dimers derived from cholesterol: synthesis and phase transitional properties

Three series of novel dimeric supramolecules, possessing both inter- as well as intramolecular H-bonding, have been prepared and investigated for their thermal properties. They were obtained in excellent yields by condensing cholesteryl ω-(3-hydroxy-4-formylphen-oxy)alkanoates with 4-(n-alkoxy)benzohydrazides, 3,4-bis(n-decyl-oxy)benzohydrazide and 3,4,5-tris(n-decyloxy)benzohydrazide. The influence of increase in the number of terminal n-alkoxy tails from one to three and the length and parity of the flexible spacer on phase transitional behaviour have been thoroughly investigated with the aid of microscopic, calorimetric and X-ray diffraction (XRD) techniques. The results of these complementary studies clearly illustrate the dependence of thermal behaviour of the dimers on these structural factors. The rigid intermolecular association via H-bonds through complementary benzohydrazide component enforce their self-assembly into frustrated and polar smectic phases; H-bond force coupled with the bulkiness of steroid moiety affects the electrical switching property of this fluid polar structure.     

Asymmetric synthesis of naturally occurring spiroketals

Spiroketals are widely found as substructures of many naturally occurring compounds from diverse sources including plants, animals as well as microbes. Naturally occurring spiroketals are biologically active and most of them are chiral molecules. This article aims at reviewing the asymmetric synthesis of biologically active spiroketals for last 10 years (1998-2007).     

Fabrication and characterization of polymer stabilized cholesteric liquid crystal cells with chiral monomers derived from borneol

Polymer stabilized cholesteric texture (PSCT) liquid crystal cells were fabricated using the commercially available host liquid crystal ZLI-2293/CB15 and functional monomers 4,4'-bis[6-(acryloyxy)hexyloxy]biphenyl (BAHB) and bornyl 4-[4-(6-acryloyloxyhexyloxy)phenylazo] benzoate. Monomers synthesized in this investigation were identified using FTIR, ¹H NMR and elemental analysis. Optical properties of the PSCT cells were studied, including variations in the reflected band, the pitch, and the helical twisting power. The dependence of the variation of liquid crystal texture on UV irradiation, temperature, and voltage were estimated. A schematic molecular orientation of the cells was used to describe the phenomena obtained on application of a voltage. Due to the thick film gap, surface stabilization from the polymer matrixes on the substrates was found to be unable to fix the focal-conic texture, even when the cell was slowly released from the applied field. The liquid crystal molecules returned to a planar texture in few seconds. The real images of reflected band colours, and the reversible changes between the turbid and transparent states corresponding to OFF (30 V) and ON (100 V) applied electric fields were evaluated.     

Liquid crystal dimers and higher oligomers: between monomers and polymers

The underlying theme of this Critical Review is the relationship between molecular structure and liquid crystalline behaviour in a class of materials referred to as liquid crystal oligomers. For the purposes of this review, a liquid crystal oligomer will be defined as consisting of molecules composed of semi-rigid mesogenic units connected via flexible spacers. Much of the review will be devoted to structure-property relationships in the simplest oligomers, namely dimers, in which just two mesogenic units are connected by a single spacer. Along the way we will see how this molecular architecture has been exploited to address issues in a range of quite different areas and has given rise to potential applications for these materials. On the whole, only compounds in which the mesogenic units are linked essentially in a linear fashion will be considered while structures such as liquid crystal dendrimers and tetrapodes fall outside the scope of this review. The review will be of interest not only to scientists working directly in this area but in particular to those interested in understanding the relationships between structure and properties in polymers, and those designing materials for new applications.     

A highly rigid diamine monomer derived from naturally occurring myo‐inositol and its use for polyamide synthesis

A rigid diamine was synthesized from myo‐inositol, a naturally occurring cyclic hexaol, and used as a monomer to synthesize polyamides. myo‐Inositol was treated with 1,1‐dimethoxycyclohexane to yield a bisketal bearing two hydroxyl groups, and from this bisketal, the target diamine was synthesized in three steps: (1) derivation of the diol into the corresponding bistriflate, (2) nucleophilic substitution of the bistriflate with sodium azide yielding a diazide, and (3) reduction of the diazide to the target diamine. The target diamine readily underwent polycondensation with dicarboxylic acid chloride in solution. The resulting polyamides, whose main chain inherited the rigid 5‐6‐5 system from the diamine monomers, have high glass transition temperatures. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3436–3443     

Photochemical synthesis of naturally occurring β-diketones

Photochemical syntheses of pongamol, ovalitenone, and milletone from the corresponding 2′-methoxychalcone epoxides are reported.     

Non-symmetric chiral isoflavone dimers: synthesis,characterisation and mesomorphic behaviour

A new series of non-symmetric chiral isoflavone-based liquid crystalline dimers, α-(2-methylbutyl-4′-(4″-phenyloxy)benzoate)-ω-(3-(4′-decyloxyphenyl)-4H-1-benzopyran-4-one-7-oxy)alkanes, with 3–12 carbon atoms in the alkyloxy spacer, have been synthesised. A pronounced odd–even effect for the phase transition temperatures upon varying the spacer length was observed. The short dimers exhibited monolayer smectic A (SmA) and smectic C (SmC*) phases while for longer homologues a chiral nematic (N*) phase was found. The temperature range of the nematic phase was broadened with elongation of the alkyl spacer. Stabilisation of the nematic phase resulted from competition between the monolayer and intercalated smectic structures. The SmA–SmC* phase transition was second order for all studied compounds with a cross over to the de Vries type behaviour for the shortest homologue.