This critical review covers the recent progress in the research of mesogen-jacketed liquid crystalline polymers (MJLCPs), special side-on side-chain liquid crystalline polymers with very short spacers or without spacers. MJLCPs can self-organize into supramolecular columnar phases with the polymer chains aligned parallel to one another or smectic phases with the backbones embedded in the smectic layers. The semi-rigid rod-like MJLCP with a tunable rod shape in both length and diameter provides an excellent building block in designing novel rod–coil liquid crystalline block copolymers which can self-assemble into hierarchical supramolecular nanostructures depending on the competition between liquid crystal formation and microphase separation (229 references).

Mesogen -jacketed liquid crystalline polymers

Several results on bent-core liquid crystals considered as new supramolecular functional materials with potential for applications are reviewed. Various topics are discussed where these materials present unique attributes with clear advantages over conventional mesogens. In particular the electrooptic responses of some mesophases are examined from the viewpoint of their possible use in electrooptic devices. Other issues are also treated such as nonlinear optical properties, flexoelectricity or the design of biaxial nematics from bent-core molecules. Future challenges and prospects for new possibilities with these materials are briefly outlined.

Bent-core liquid crystals in the route to functional materials

The liquid-crystalline (LC) phase structures and transitions of a combined main-chain/side-chain LC polymer (MCSCLCP) 1 obtained from radical polymerization of a 2-vinylterephthalate, poly(2,5-bis{[6-(4-butoxy-4′-oxybiphenyl) hexyl]oxycarbonyl}styrene), were studied using differential scanning calorimetry, one- and two-dimensional wide-angle X-ray diffraction (1D and 2D WAXD), and polarized light microscopy. We have found that 1 with sufficiently high molecular weight can self-assemble into a hierarchical structure with double orderings on the nanometer and subnanometer scales at low temperatures. The main chains of 1, which are rodlike as a result of the “jacketing” effect generated by the central rigid portion of the side chains laterally attached to every second carbon atom along the polyethylene backbone, form a 2D centered rectangular scaffold. The biphenyl-containing side chains fill the space between the main chains, forming a smectic E (SmE)-like structure with the side-chain axis perpendicular to...

Hierarchical supramolecular ordering with biaxial orientation of a combined main-chain/side-chain liquid-crystalline polymer obtained from radical polymerization of 2-vinylterephthalate.

A series of new monomers of 2,5-bis[(4-tertbutyl-phenyl)-1,3,4-oxadiazole] styrene (M-Ct) and 2,5-bis[(4-alkoxy-phenyl)-1,3,4-oxadiazole]styrene (M−OCm, m is the number of the carbons in the alkoxy groups, m = 8, 10, 12, 14) were synthesized. Conventional radical polymerization of the monomers resulted in a series of new mesogen-jacketed liquid crystalline polymer (MJLCP) containing the 1,3,4-oxadiazole unit. The chemical structures of the monomers were confirmed by elemental analysis, mass spectrometry, 1H NMR, and IR. The molecular characterization of the corresponding polymers of P-Ct and P-OCms was performed with 1H NMR, gel permeation chromatography, and thermogravimetric analysis. Their phase structures and transitions were investigated by differential scanning calorimetry, wide-angle X-ray diffraction, and polarized light microscopy experiments. The P-Ct formed the hexatic columnar nematic (ΦHN) phase that is typical for MJLCPs, wherein the chain molecules were rodlike. The P-OCms exhibited a well-...

Synthesis and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers Containing 1,3,4-Oxadiazole Based Side Chains

We report the synthesis and characterization of a series of novel mesogen- jacketed liquid-crystalline polymers, poly(2,5-bis(4 0 -alkoxycarbonylphenyl)styrene)s (1-m, where m is the number of carbon atoms in the alkyl tails), along with the corre- sponding monomers, 2,5-bis(4 0 -alkoxycarbonylphenyl)styrenes (2-m), and their precur- sors, 2,5-bis(4 0 -alkoxycarbonylphenyl)toluenes (3-m). The influence of the tail length on the thermotropic properties of the two types of low-molecular-mass compounds and macromolecules was investigated with a combination of differential scanning calorime- try, polarized optical microscopy, and wide-angle X-ray diffraction techniques. Except for compound 3-3, which exhibited a monotropic nematic phase, all members of the low-molar-mass molecules developed no mesophase during both heating and cooling processes. The glass-transition temperatures of the polymers decreased as the tail lengths increased. The 5% weight loss temperatures of all the polymers under a nitro- gen atmosphere were above 360 8C, indicating quite high thermal stability. Although polymers 1-1 and 1-2 were non-liquid-crystalline, columnar nematic phases were observed for the remaining homopolymers with longer alkyl tails. The mesophases of 1-3 to 1-9 that developed at high temperatures remained upon cooling to room temper- ature, whereas those of 1-10 to 1-12 disappeared during the cooling process. V C 2007

Synthesis and characterization of a thermotropic liquid‐crystalline poly[2,5‐bis(4′‐alkoxycarbonylphenyl) styrene]

We report the design, synthesis, and characterization of a series of mesogen-jacketed liquid crystalline polymers with bent-core liquid crystals (BCLCs). For the first time, BCLC mesogens were directly side-attached to the polymer backbone and bent-core mesogen-jacketed liquid crystalline polymers (BMJLCPs) were achieved. Both three-ring and five-ring mesogens were employed. The n-alkoxy substituent lengths for the three-ring and five-ring BMJLCPs were controlled as n = 1−5 and n = 6−16, respectively. Various characterization techniques such as differential scanning calorimetry, wide-angle X-ray diffraction, and polarized light microscopy were used to study their mesomorphic phase behavior. The monomers of five-ring BMJLCPs with relatively long tails showed mesophase behavior. Columnar liquid crystalline phase was observed in both three-ring and five-ring BMJLCPs. Columnar rectangular (ΦR) phase was observed in the three-ring system. In the five-ring BMJLCPs, relatively short-tail homologues possess ΦR ph...

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Design, Synthesis, and Characterization of Bent-Core Mesogen-Jacketed Liquid Crystalline Polymers

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Design, Synthesis, and Characterization of Bent-Core Mesogen-Jacketed Liquid Crystalline Polymers