A. Yu. Bobrovsky

Liquid crystalline carbosilane dendrimers: First generation

Abstract An approach to the synthesis of a new class of liquid crystalline (LC) compounds, dendrimers of regular structure with terminal mesogenic groups, was elaborated. LC dendrimers based on the carbosilane dendritic matrix of first generation were synthesized. Cyanobiphenyl, methoxyphenyl benzoate and cholesteryl groups were used as mesogenic fragments. Individuality and structure of all compounds obtained was proved by GPC together with 1H- and 29Si NMR methods. The mesomorphic behaviour and structure of the LC dendrimers synthesized were investigated. It is argued that different mesophases of the smectic type are realized in all cases. It is shown that the mesophase type of these compounds essentially depends on the chemical nature of the mesogenic groups.

New Chiral Nematic Materials with Photovariable Helical Supramolecular Structure for Reversible Optical Data Recording

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Photochromism in mixtures of liquid crystalline chiral copolymers with a photosensitive chiral dopant

Mixtures of a photosensitive chiral dopant based on (—)-menthone with left-handed and righthanded cholesteric copolymers were prepared. The phase behaviour and optical properties of the mixtures prepared were studied. The action of UV radiation on planar oriented films of such systems was shown to induce dramatic changes in the maximum reflection wavelength as a result of E-Z isomerization of the dopant molecules. The kinetics of photoisomerization of such mixtures in solution and in the bulk were investigated at different temperatures. The above mixtures can be considered as promising and uprecedented materials for coloured data recording and storage.

Phase diagrams and optical properties of new menthyl-containing LC copolymers forming chiral mesophases

New comb-shaped LC copolymers based on phenyl benzoate and menthyl-containing monomers were synthesized. Phase behaviour, optical properties and structure of the synthesized copolymers with different compositions were studied. Specific features of the development of helical nematic and smectic mesophases (N*, NB*, Ncyb*, Nre*, SmA*, SmF*, blue phases) were revealed. Special attention was paid to studying the structure and optical properties of the new chiral NB* mesophase. For this unusual type of mesophase, a model accounting for the arrangement of the mesogenic group is suggested. It is stressed that the subscript B does not mean biaxial (a biaxial N phase is usually denoted Nb) and B refers to the hexagonal ordering of the side groups, similar to that in a SmB phase. An alternative nomenclature would be Nh, where subscript h refers to hexagonal as in Colh0 for a hexagonally ordered columnar phase of a discogen.

Induction of the cholesteric mesophase in hydrogen-bonded blends of polymers with a low molecular mass chiral dopant

A family of new hydrogen bonded complexes based on comb-shaped LC copolymers containing alkyloxy-4-oxybenzoic acid mesogenic fragments and chiral dopant molecules, derivatives of pyridine-4-carboxylic acid has beenprepared. At concentrations of chiral groups in the range 1± 25 mol%, induction of the cholesteric phase is observed. The temperature .

New chiral photochromic menthone-containing homopolymers and copolymers - synthesis, phase behaviour and photo-optical properties

A new approach for the preparation of photosensitive materials for coloured data recording and storage is advanced. This approach involves the synthesis of copolymers containing nematogenic and combined (-)-arylidene-p-menthan-3-one chiral photochromic fragments in one monomer unit. The conditions for the formation of an LC phase in the chiral photochromic homopolymers as a function of the structure of the side groups have been identified; for a new series of copolymers, the effect of their composition on the phase behaviour and photooptical properties is considered. Planarly oriented films of the copolymers show selective light reflection in the UV, visible, and near IR spectral regions. The photochemical behaviour of the homopolymers and copolymers in dilute solution and as films has been studied. In these systems, under UV radiation, the E-Z isomerization of the (-)-arylidene-p-menthan-3-one fragment is the dominating process. The kinetic features of the photoprocess are revealed, and the effective qua...

Cholesteric mixture containing a chiral azobenzene-based dopant: material with reversible photoswitching of the pitch of the helix

A new low molar mass chiral-photochromic dopant was synthesized. It contains a menthyl fragment as the chiral group and an azobenzene group, capable of E - Z photoisomerization, as the photochromic component. The substance obtained was used as a chiral dopant in mixtures with a comb-shaped cholesteric acrylic copolymer with menthyl-containing chiral side groups and phenyl benzoate nematogenic side groups. Such mixtures form a cholesteric mesophase. The chiral dopant led to an additional twisting of the cholesteric helix, i.e. to a shift of the selective light reflection peak to a shorter wavelength region of the spectrum. The initial copolymer gave selective light reflection in the spectral range 1200-1400 nm; the mixture containing 3.5 mol % of chiral-photochromic dopant reflects light with λmax~ 850 nm. The action of light with λir~ 440 nm results in E - Z isomerization of the azo-group of the chiral dopant and in a shift of the selective light reflection peak to the long wavelength region of the spectrum (amplitude of shift = 30 nm). This is explained by a lower helical twisting power of the Z-isomer of the chiral dopant. This process is thermally reversible: annealing of irradiated films leads to a back shift of the selective light reflection peak to the short wavelength region of the spectrum due to Z - E isomerization. Kinetic features of the direct and backward processes of isomerization were studied: it was shown, that mixtures of the chiralphotochromic azobenzene-containing dopant with cholesteric polymers give new possibilities for the creation of polymer materials with a reversibly regulated helical supramolecular structure which determines their optical properties.

Interaction of light with a NLC–dendrimer system

The interaction of light with a nematic liquid crystal (NLC) doped with dendrimers containing terminal light-absorbing azobenzene fragments and a low-molar-mass dye identical to the fragments was studied in detail. Both the dendrimers and the dye induce orientational nonlinearity in a transparent nematic host. For the fifth-generation dendrimer, the nonlinearity is negative (director is rotated away from the light field direction). For the first-generation dendrimer and the dye, the nonlinearity sign depends on the light propagation direction with respect to the NLC director, light polarisation and external electric field. The results obtained show that complication of the molecular structure of the dopant, i.e. passing from the ‘free’ dye molecule to the first- and fifth-generation dendrimers, results in an increase of the efficiency of the orienting effect of the light.

Light-Induced Director Reorientation in Nematic Liquid Crystals Doped with Azobenzene-Containing Macromolecules of Different Architecture

The results of the studies of the orientational optical nonlinearity of a nematic host doped with high-molar-mass compounds of different molecular architecture such as a comb-like polymer and a dendrimer containing azobenzene chromophores are presented. The nonlinearity induced by these compounds was found to be higher than that induced by the low-molar-mass dyes similar in structure to the light-absorbing constituents of the polymer and dendrimer. Possible reasons for the nonlinearity enhancement for macromolecular dopants are discussed.

Orientational optical nonlinearity induced by comb-shaped polymers in a nematic liquid crystal

The effect of optical orientation in nematic liquid crystals containing small additions of high-molecular compounds, i.e., comb-shaped polymers with light-absorbing azobenzene side fragments, was studied. The effects of light-induced reorientation of the director of nematic liquid crystals caused by light absorption of polymers and a low-molecular compound with a structure similar to side fragments of the polymers were compared in detail. An explanation was proposed for large values of the orientational nonlinearity induced by polymers.