Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.

Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units.

Photopatterning of Azobenzene-Containing Liquid Crystalline Triblock Copolymers: Light-Induced Anisotropy and Photostabilization.

Photochromic liquid crystalline block copolymers (PLCBCs) are currently playing a significant role as light-responsive materials because of their light controllable features over multiple length scales. Herein, a study of the photoinduced optical anisotropy derived by the combination of orientation phenomena at molecular and supramolecular levels in a novel kind of side-chain PLCBCs with mesogenic phenyl benzoate groups and pyridine units that is hydrogen bonded with azobenzene-containing phenol is reported. Based on the polymeric architectures and composition, the supramolecular configuration self-organizes in different microphases that affect the material response to the external stimuli.

Hybrid fluorescent liquid crystalline composites: directed assembly of quantum dots in liquid crystalline block copolymer matrices.

Hybrid fluorescent liquid crystalline (LC) composites containing inorganic quantum dots (QDs) are promising materials for many applications in optics, nanophotonics and display technology, combining the superior emission capability of QDs with the externally controllable optical properties of LCs. In this work, we propose the hybrid LC composites that were obtained by embedding CdSe/ZnS QDs into a series of host LC block copolymers of different architectures by means of a two-stage ligand exchange procedure. The ABA/BAB triblock copolymers and AB diblock copolymers with different polymerization degrees are composed of nematogenic phenyl benzoate acrylic monomer units and poly(4-vinylpyridine) blocks, which are capable of binding to the QD surface.

Phase Structure Recording in a Nematic Side-Chain Liquid-Crystalline Polymer.

Dye-doped nematic side-chain liquid-crystalline polymers possess extraordinary large optical nonlinearity and ability to store the induced orientational deformations in a glassy state, which makes them a very promising material for photonic applications. In this study, the phase structures were generated and recorded in the bulk of a 50-μm layer of a nematic liquid-crystalline side-chain polymer, containing polyacrylate backbone, spacer having five methylene groups, and phenyl benzoate mesogenic fragment. The polymer was doped with KD-1 azodye.

Polarization Gratings in Azobenzene-Based Fully Liquid Crystalline Triblock Copolymer.

Photosensitive liquid crystalline (LC) block copolymers are a universal platform for designing functional materials for optics and photonics. Here, azobenzene LC ABA triblock copolymer containing mesogenic groups in each block is studied as a medium for the recording of polarization holographic gratings. The fast recording of polarization gratings is successfully performed with two orthogonally circularly polarized light beams of a 532-nm laser.

Optical orientation of nematic liquid crystal droplets via photoisomerization of an azodendrimer dopant.

Two sequential transformations of the orientational structure in nematic liquid crystal droplets containing a dendrimer additive (nanosized macromolecules with light-absorbing azobenzene terminal moieties) under light irradiation in the UV-blue spectral range were investigated. The origin of these transitions is in the change of the boundary conditions due to photoisomerization of the dendrimer adsorbed onto the liquid crystal-glycerol interface. It was shown that the photoisomerization processes of dendrimer molecules in a liquid crystal are accompanied by a spatial rearrangement of their azobenzene moieties, which is the key point in the explanation of the observed effects.

Communication: Orientational structure manipulation in nematic liquid crystal droplets induced by light excitation of azodendrimer dopant.

Reversible orientational transitions in the droplets of a nematic liquid crystal (NLC) caused by the change of boundary conditions under the low intensity diode illumination are investigated. Photosensitivity of NLC is achieved by the addition of the dendrimer compound with azobenzene terminal groups. Two types of NLC droplets in glycerol are considered: the spherical droplets in the bulk of glycerol and the droplets laid-down onto the solid substrate.

Unexpected Temperature Behavior of Polyethylene Glycol Spacers in Copolymer Dendrimers in Chloroform.

We have studied copolymer dendrimer structure: carbosilane dendrimers with terminal phenylbenzoate mesogenic groups attached by poly(ethylene) glycol (PEG) spacers. In this system PEG spacers are additional tuning to usual copolymer structure: dendrimer with terminal mesogenic groups. The dendrimer macromolecules were investigated in a dilute chloroform solution by (1)H NMR methods (spectra and relaxations).

Average relaxation time of internal spectrum for carbosilane dendrimers: nuclear magnetic resonance studies.

A new theoretical description of the interior mobility of carbosilane dendrimers has been tested. Experiments were conducted using measurements of the (1)H NMR spin-lattice relaxation time, T(1H), of two-, three- and four-generation carbosilane dendrimers with three different types of terminal groups in dilute chloroform solutions. Temperature dependences of the NMR relaxation rate, 1/T(1H), were obtained for the internal CH(2)-groups of the dendrimers in the range of 1/T(1H) maximum, allowing us to directly evaluate the average time of the internal spectrum for each dendrimer.

NMR studies of carbosilane dendrimer with terminal mesogenic groups.

The 4-generation carbosilane dendrimer with terminal cyanobiphenyl mesogenic groups in dilute solution of CDCl(3) was investigated using (1)H NMR technique. The spectrum was obtained and the relaxation time, T(1), was measured in the temperature range 320-225 K. For the first time, the extrema of T(1) values were achieved for majority of the dendrimer functional groups.

Order and dynamics of a liquid crystalline dendrimer by means of 2H NMR spectroscopy.

A complete Deuterium NMR study performed on partially deuterated liquid crystalline carbosilane dendrimer is here reported. The dendrimer under investigation shows a SmA phase in a large temperature range from 381 to 293 K, and its mesophasic properties have been previously determined. However, in this work the occurrence of a biphasic region between the isotropic and SmA phases has been put in evidence.

Liquid crystal codendrimers with a statistical distribution of phenolic and mesogenic groups: behavior as Langmuir and Langmuir-Blodgett films.

The first series of carbosilane liquid crystal codendrimers with groups of different polarity has been synthesized. The chemical structure of the newly synthesized materials and the composition of the codendrimers were studied by NMR spectroscopy and MALDI-TOF MS. It was found that the codendrimers tend to form stable Langmuir films at the air-water surface.