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In a narrow temperature window in going from the isotropic to highly chiral orders, cholesteric liquid crystals exhibit so-called blue phases, consisting of different morphologies of long, space-filling double twisted cylinders. Those of cubic spatial symmetry have attracted considerable attention in recent years as templates for soft photonic materials. The latter often requires the creation of monodomains of predefined orientation and size, but their engineering is complicated by a lack of comprehensive understanding of how blue phases nucleate and transform into each other at a submicrometer length scale. In this work, we accomplish this by intercepting nucleation processes at intermediate stages with fast cross-linking of a stabilizing polymer matrix. We reveal using transmission electron microscopy, synchrotron small-angle X-ray diffraction, and angle-resolved microspectroscopy that the grid of double-twisted cylinders undergoes highly coordinated, diffusionless transformations. In light of our findings, the implementation of several applications is discussed, such as temperature-switchable QR codes, micro-area lasing, and fabrication of blue phase liquid crystals with large domain sizes., The arrangements of defect lines in liquid crystal blue phases provide promising templates for photonic crystals. Here Liu et al. investigate in detail how inter-phase transitions proceed, by intercepting nucleation with on-demand cross linking of a supporting polymer matrix.

We have investigated the photoresponsive behavior of homogeneously aligned low-azobenzene-concentration crosslinked liquid-crystalline polymers. We compared the thermal contraction and photocontraction of the films, and show that upon UV irradiation, they bend efficiently towards the actinic light source. The photoinduced bending is studied both under continuous-wave irradiation and irradiation with nanosecond pulses. Pulsed irradiation revealed that the photomechanical response can take place within sub-millisecond time scale, and that even a single laser pulse can cause the sample to bend.

Crosslinked azobenzene liquid-crystalline polymer films have been prepared by in-situ photopolymerization, and their photoinduced changes in birefringence and stress on macroscopic motion were investigated. Upon exposure to UV light, the film bent toward an actinic light source along the rubbing direction, and the bent film also reverted to the initial flat state after exposure to visible light at room temperature. Moreover, the birefringence simultaneously decreased and the stress was generated upon UV irradiation. These results indicate that the molecular alignment in the film becomes disordered by trans-cis photoisomerization of the azobenzene moieties and the resultant contraction of the film generates the stress.

We prepared crosslinked azobenzene liquid-crystalline polymer brushes on flexible polymer films by surface-initiated atom transfer radical polymerization and a subsequent crosslinking reaction. Reversible isomerization of azobenzene moieties was observed in the crosslinked films upon irradiation with UV and visible light. Upon exposure to linearly polarized UV light, the films bent slightly along the polarization direction of light toward an actinic light source. After turning off the UV light, the films maintained the bent shape, and then reverted to the initial form by irradiation with visible light. We have successfully developed a novel photomobile material with crosslinked azobenzene liquid-crystalline polymer brushes.

Fabrication of a microlens array film was explored by means of photoinduced reorientation of dye-doped polymerizable liquid crystals (LCs). LC monomer/photoinitiator mixtures doped with a small amount of an oligothiophene derivative were irradiated with a 488-nm beam from an Ar+ laser. Then the sample cell was periodically moved. After these two processes were repeated for a few tens times, remaining photoinitiators were quenched by irradiation with UV light. Observation of the cells with a polarizing optical microscope revealed that the molecular alignment of LCs induced by the Ar+ laser beam remained unchanged after the beam was turned off and a microlens array with a square-lattice type was obtained. This indicates that formation of the microlens and photopolymerization of the LC monomers are brought about simultaneously in a small area. The fabricated microlens has polarization selectivity that reflects molecular alignment. The focal length of the microlens arrays could be changed by controlling the i...

To precisely control the first-order diffraction efficiency of holographic gratings recorded in an amphiphilic diblock liquid-crystalline copolymer P40A37, effect of recording time on grating formation and enhancement was studied systematically. Several parameters such as surface relief, the first-order diffraction efficiency, the maximum transmittance under an optical polarizing microscope and order parameters of grating samples were evaluated before and after annealing. Then the enhancement coefficient with recording time was estimated. The best enhancement effect was obtained at 10-s recording upon nano-scaled phase separation. By precisely adjusting the recording time, the diffraction efficiency of holographic gratings in P40A37 can be finely controlled from 0.13% to 10%.

After being pre-treated upon irradiation of unpolarized light at 366 nm, an azobenzene-containing liquid-crystalline polymer film was photoinduced alignment by one linearly polarized laser beam at 488 nm, leading to a large birefringence of 0.21. Then holographic gratings were recorded in the pre-irradiated polymer films by interference of two coherent laser beams. Little surface relief was obtained by the holographic recording process, indicating that a refractive-index grating paid most of contributions to the diffraction efficiency. Because the cooperative motion of the azobenzene mesogens were eliminated in the cis-azobenzene-rich isotropic film by the pre-irradiation, multi-processes of the refractive-index gratings were successfully achieved. The obtained grating structures were clearly shown in the polarizing optical microscopic pictures, which were also verified by their diffraction patterns. The azobenzene-containing liquid-crystalline polymer used in this study has potential application in high-...

Grating waveguide couplers with a flat surface were fabricated in an azobenzene liquid-crystalline polymer film by holographic lithography using Ar + laser beams at 488 nm. When a probe beam at 633 nm was incident to one grating of a grating waveguide coupler, the beam propagated in the waveguide and an output beam came out from the other grating with the throughput coupling efficiency of ≈5%. Upon irradiation of the film between two gratings with UV light to cause trans-cis photoisomerization of the azobenzene moiety, the intensity of the output beam was repeatedly switched. It was found that the alternating irradiation at 366 and 436 nm induced reversible changes in the intensity of the guided probe beam.

An amphiphilic diblock liquid-crystalline copolymer consisting of poly(ethylene oxide) (PEO) and polymethacrylate containing an azobenzene moiety in the side chain was prepared by atom transfer radical polymerization (ATRP). The specifically-designed chemical constitution and the low molecular-weight polydispersity enable the block copolymer to form a regular microphase-separated nanostructure self-assembled in its bulk films, in which a hexagonal packing of the PEO cylinders normal to the substrates was dispersed in a continuous phase of azobenzene mesogens with out-of-plane alignment. Then a commerically available rubbing technique was first used to control the microphase-separated domains in the copolymer films. By introducing novel supramolecular cooperative motions between ordered azobenzene mesogens and PEO microphase domains, macroscopic array of PEO nanocylinders was regularlly formed along the rubbing direction. Both the dotted and parrallel stripe patterns of PEO nanocylinders were successfully ...

Highly birefringent liquid-crystalline polymers (LCPs) containing an azobenzene group directly connected to a tolane moiety (azotolane moiety) were synthesized. Attention was focused on the effect of the position of the tolane moiety in the mesogenic azotolane group and the donor−acceptor substituent on photochemical phase transition behavior. In solution, cis−trans back-isomerization of the LCP containing azotolane moieties with a donor−acceptor was faster than that of LCPs having no acceptor groups. All the LCP films showed a homogeneous alignment and very high values of birefringence (about 0.4 at 633 nm). In the LCPs with a conventional azotolane moiety, a large change in birefringence (above 0.35) was induced repeatedly by irradiation of UV light. Furthermore, we investigated photoswitching behavior at telecommunication wavelength (1550 nm) based on the photochemical phase transition by irradiation of UV light.

One- and two-photon induced phase transition behavior of low-molecular-weight and polymer liquid crystals (LCs) was observed. When a photochemical reaction of a two-photon absorbing dye was induced in a nematic (N) LC, N-to-isotropic (I) phase transition was induced with high spatial resolution. As a result of the phase transition, the refractive index of the materials was changed by two-photon processes. Furthermore, the I phase induced in the polymer LC was thermally stable and it still appeared after heating above N–I phase transition temperature. The results reported here are the first observation of the photochemical phase transition of the LCs induced by a two-photon process.

In order to lower the operating voltage of molecularly doped electroluminescent (EL) devices using a low-molecular-weight liquid crystal (LC), we added a small amount of electrolytes (tetrabutylammonium bromide: TBAB) to the EL devices. The addition of TBAB decreased the driving voltages by one order of magnitude. Furthermore, the EL devices containing TBAB could be operated under not only a dc mode but also an ac mode. It has become apparent that the emission intensity increases in the order of smectic A phase

Group 4 [η1:η3-tert- butyl(dimethylfluorenylsilyl)amido]dimethyl complexes [t-BuNSiMe 2Flu]MMe2 (M = Ti, 1; Zr, 2; Hf, 3) were synthesized in a one-pot synthesis starting from the ligand, MeLi and MCl4 (M = Ti, Zr, Hf), respectively. The structures of these complexes were determined by X-ray crystallography and the results obtained revealed that the fluorenyl ligand coordinates to center metal in a η3-manner irrespective of center metal employed. Propylene polymerization was conducted at 0 or 20 °C in toluene by 1-3 combined with dried methylaluminoxane (MAO), which was prepared from the toluene solutions of MAO by removing free trialkylaluminiums, and HNMe2PhB(C6F5)4 in the presence of triisobutylaluminium. The 1-dried MAO system gave the polymer with syndiotactic triad (rr) of 63 0x1.e2fc8p-891t 0 °C, whereas 2 and 3 did not give any polymer in the same conditions. The 2-dried MAO system gave the polymer with the highest syndiotacticity (rr = 97%) at 20 °C, although the activity was low. The 3-dried MAO system did not give any polymer even at 20 °C. When HNMe2PhB(C6F5)4 was used in place of dried MAO at 20 °C, 1 gave almost atactic polymer, while 2 and 3 gave highly syndiotactic one (rr > 90%). These results indicate that the catalytic performance strongly depended on the center metal of the ansa- fluorenylamidodimethyl complexes as well as cocatalysts employed.

The photoinduced reorientation behavior of dye-doped nematic liquid crystals (LCs) was investigated. Thiophene derivatives with ester moieties were newly synthesized as the guest dye molecule. The liquid-crystalline behavior and optical properties of these compounds were evaluated, and the effect of the dye structure on the photoinduced reorientation behavior of the dye-doped LCs was investigated. The photoinduced formation of diffraction rings was observed as a result of the self-phase modulation effect at the intensity of 11 W/cm2, when an Ar+ laser beam at 488 nm was irradiated above the threshold intensity. Comparison of the lowest threshold light intensity for the appearance of the diffraction rings revealed that the thiophene dye with ester moieties directly bound to the terminal thiophene shows a lower threshold intensity than those of any other dyes.

Based on a hydrophilic poly(ethylene oxide) macroinitiator (PEOBr), a novel amphiphilic diblock copolymer PEO-block-poly(11-4-cyanobiphenyloxy)undexyl) methacrylate) (PEO-b-PMA(11CB) was prepared by atom transfer radical polymerization (ATRP) using CuCl/1,1,4,7,10,10-hexamethyltriethylenetriamine as a catalyst system. An azobenzene block of poly (11-[4-(4-butylphenylazo)phenoxyl]undecyl methacrylate) was then introduced into the copolymer sequence by a second ATRP to synthesize the corresponding triblock copolymer PEO-b-PMA(11CB)-b-PMA(11Az). Both of the amphiphilic block copolymers had well-defined structures and narrow molecular-weight distributions, and exhibited a smectic liquid-crystalline phase over a wide temperature range.

Azobenzene liquid-crystalline elastomer (LCE) films with homeotropic alignment were prepared by in-situ photopolymerization of mixtures of an LC monomer and a cross linker, both of which contain azobenzene chromophores. Thermodynamic and mesomorphic properties of the monomers and the LCE films were determined by differential scanning calorimertry and polarizing optical microscopy. X-ray diffraction patterns revealed that the LCE films show a smectic A phase. Polarized UV spectra and conoscopic observation with a polarizing optical microscope demonstrated that the azobenzene mesogens are aligned homeotropically in the films.

Copolymerization of propene and norbornene (P−N) was conducted with (t-BuNSiMe2Flu)TiMe2 (1) activated by Me3Al-free methylaluminoxane (dried MAO), modified methylaluminoxane (MMAO), and Ph3CB(C6F5)4/Oct3Al at 20 °C under atmospheric pressure of propene. The 1−Ph3CB(C6F5)4/Oct3Al system showed the highest activity and gave the copolymer with the lowest molecular weight and broad molecular weight distribution. The 1−dried MAO system produced the copolymer with the narrowest molecular weight distribution. The detailed investigation of this system clarified that the norbornene content in the copolymer was almost proportional to the N/P feed ratio with a narrow polydispersity of 1.1−1.2 and the glass transition temperatures of the P−N copolymers increased linearly against the norbornene content in the copolymers, that is, 53 °C with 17 mol % of norbornene and 249 °C with 71 mol % of norbornene. The 13C NMR spectra also suggested the random distribution of the comonomers in the copolymers obtained.

Cross-linked liquid-crystalline polymer films were prepared by polymerization of mixtures containing azobenzene monomers and cross-linkers with azobenzene moieties. Two types of the cross-linked liquid-crystalline polymer films were prepared: monodomain films and polydomains films. Photoirradiation of the monodomain films with UV linearly polarized light (LPL) gave rise to bending of the films toward actinic light along the polarization direction, when the light polarization was parallel to the rubbing direction. When the two directions were perpendicular to each other, the bending was isotropic without a preferential direction. On the other hand, exposure of the polydomain films to UV LPL led to bending of the films always along the polarization direction of the actinic light. This means that one can induce bending of the film along any direction precisely by choosing the polarization direction of the actinic light.

Optical switching of a 1.55-μm laser beam was explored by means of photochemical phase transition of polymer and low-molecular-weight azobenzene liquid crystals (LCs). It was observed that the 1.55-μm laser beam could be repeatedly switched by turning on and off the actinic light, and a large change in refractive index was induced in the azobenzene LCs at the near infrared region. It was also found that controlling the thickness of LCs could enhance the change in the transmittance of the 1.55-μm laser.

A series of poly(alkyl methacrylate)s having azobenzene and cyanobiphenyl moieties were synthesized and their optical properties were characterized. The effect of content of the photosensitive unit and the length of alkyl chain of a transparent unit on the photoresponsive alignment behavior was investigated. The azobenzene monomer (photoresponsive unit), the cyanobiphenyl monomer (mesogenic unit), and the alkyl methacrylate monomers with methyl, ethyl, n-butyl, hexyl or lauryl group (transparent unit) were copolymerized to yield transparent polymer films. Upon irradiation of LPL at 488 nm, a uniaxial optical anisotropy was generated due to the molecular alignment. The photoinduced alignment behavior was strongly dependent on the alkyl chain length and the intensity of the actinic light.

Recent progress in alignment modulation of azobenzene-containing liquid crystal systems by photochemical reactions has been reviewed by dividing the modulation methods into two types: phase transitions (order–disorder change) and change of liquid crystal directors (order–order change). First, photochemical phase transitions and alignment changes of liquid crystals in guest/host mixtures and polymers are summarized. Then, alignment control of liquid crystals by linearly polarized light and photoactive surface layers is discussed. Finally, recent applications of alignment change and photochemical phase transitions of liquid crystals in holographic technology and photomechanical effects are introduced. In addition, future possible applications for a variety of practical devices, such as display devices, optical switching and reversible optical image storage, are mentioned.

Modified methylaluminoxane (MMAO), from which free AlMe 3 and Al(iBu) 3 were reduced to ca. 0.1 mol-%, was supported on metal oxides, such as anhydrous silica gel, alumina, or magnesia; the metal oxide-supported MMAO prepared were used as cocatalysts for propylene polymerization combined with a chelating (diamide)dimethyltitanium) complex. The systems conducted living polymerization of propylene at 0°C regardless of the support for MMAO. The propagation rate constants (k p ) of the systems and the molecular weight distribution (M w /M n ) of the produced polymer depended on the metal oxide employed. The XPS analysis of the supported MMAOs suggested that the k p value increased with the Lewis acidity of MMAO on the support and the broadening M w /M n was ascribed to the distribution of k p caused by the heterogeneity of the supported cocatalyst.

Propylene polymerization was conducted at 0 °C in heptane or chlorobenzene (CB) by an ansa-fluorenylamidodimethyltitanium complex combined with dried, modified methylaluminoxane that had been treated by dilution with heptane and successively repeatedly vacuum dried to remove any free tdalkylaluminiums. The post-polymerizations testified that the living polymerization proceeded irrespective of the solvent used. The heptane system gave the syndiotactic poly(propylene)s (PPs), whereas the CB system gave almost atactic PPs. After the first polymerization in heptane had been completed, the same amounts of propylene and CB were added for the second polymerization. This procedure gave the syndiotactic-atactic stereoblock PP with narrow molecular-weight distributions.

A new class of photo- and electroactive polymer materials showing an liquid-crystalline (LC) phase were designed and synthesized: four kinds of polymers with both oxadiazole and arylamine moieties as carrier-transporting groups in the side chain. Among them, the polymers with a dimethylamine and a methylcarbazole moiety show LC phases. Furthermore, all the polymers emitted strong blue fluorescence, and their fluorescent quantum yields were over 0.6. The aligned sample of the polymer with the carbazole moiety emitted polarized fluorescence at room temperature. One-layer type electroluminescent (EL) devices were fabricated by using the polymer with a triphenylamine moiety, which exhibited the highest quantum yield (∼0.82), and found to emit the EL emission at blue region.

Formation of gratings by means of the photoinduced alignment change of polymer liquid crystals (PLCs) has been explored in a glassy state. To obtain high diffraction efficiency (η), we synthesized highly birefringent PLCs containing an azobenzene group directly connected with a tolane moiety (3ATm), in which the alkyl spacer length ( CH 2)m was varied as m=6, 9 and 12. It was found that the values of birefringence in all the PLCs were about 0.4. The behaviors of the photoinduced alignment change and the formation of gratings were found to be dependent on the alkyl spacer length of 3ATm.

Electrochemical and electroluminescent (EL) properties of a polymer liquid crystal (PLC) composed of an oxadiazole moiety as an electron-transporting unit and an amine moiety as a hole-transporting...

Electroluminescent (EL) properties of a low-molecular-weight liquid crystal (LC), which is composed of an oxadiazole moiety as an electron-transporting unit and an amine moiety as a hole-transporting unit, were investigated. The most significant characteristic of the LC is to possess bipolar carrier-transporting abilities. The bipolar LC makes it possible to fabricate a simple EL device. We fabricated an EL device (cell gap: 2 μm) with configuration of indium tin oxide (ITO)/LC/MgAg. The device emitted visible light at above 10 V. In particular, the values of luminance and current density of an EL device containing poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT) as a hole-injecting layer were ten and six times higher than those of the ITO/LC/MgAg device without the PEDOT layer, respectively. Furthermore, surfaces of the glass substrate with an ITO electrode and a PEDOT layer were rubbed to align mesogens. Dichroic ratio of the emission from an ITO/rubbed PEDOT/LC/MgAg device was estima...

Propene polymerization was conducted at 0 °C by [t-BuNSiMe2Flu]TiMe2 combined with B(C6F5)3, MAO, or the MAO which had been dried in a vacuum and washed with hexane before use. The effect of cocata...

Formation of intensity gratings was studied with two s‐polarized (s+s) configuration in polymer liquid crystals (PLCs) containing a photochromic moiety (azobenzene) and a mesogenic unit (tolane, T‐...

Polar order in the phosphonium liquid crystal thin films, which are composed of two-dimensional ion-pair-based domains separated by the insulating hydrocarbon layers, was probed by second harmonic generation (SHG) analysis. Despite the ordinary amphiphilic self-assemblies containing no pi-electron moieties, the solid-state thin films retaining a smectic layer structure showed clearly an SHG activity, while the disordered films without the layer structure were not active at all for the SHG. It was found that the multilayer structure plays a crucial role for the SHG from the phosphonium thin films and the ionic layers act as an SHG-active site. The most significant characteristic of this system is to possess an ability to control SHG intensity electrically. The efficiency of the SHG process in the thin-film assemblies was enhanced by applying an external electric field parallel to the layer plane. Furthermore, through evaluation of thermal stability of the sample films, it was revealed that the SHG signals were detected only in the solid-state temperature range and the disappearance of the SHG occurs earlier than the solid-to-liquid crystalline phase transition. These results demonstrated that the origin of polar order in the phosphonium thin films is due to in-plane noncentrosymmetric arrangement (ferroelectric ordering) of ion pairs as an electric dipole, that is, dipole symmetry in an ionic layer.

The composition of a crosslinked azobenzene liquid-crystalline polymer and a flexible polymer film can provide a variety of simple devices that can walk in one direction like an ‘inchworm’ and move like a ‘robotic arm’ induced by light.

The excited-state S 2 dynamics of an azobenzene derivative, trans-BMAB, was investigated in solution by femtosecond transient absorption and picosecond single-photon timing fluorescence spectroscopies. The fluorescence was observed at 400 nm with a lifetime ∼250 fs. The S 1 state with an absorption maximum at 410–415 nm was formed with a time constant of ∼250 fs from the S 2 state followed by relaxation with a lifetime of ∼2.3 ps in n -hexane. The stimulated emission from the S 2 state overlapped with the femtosecond transient absorption spectra just after excitation, which was confirmed by polarization absorption spectroscopy.

Optical switching behavior of polymer azobenzene liquid crystal (LC) was investigated by the use of reflection-mode analysis. Intensity of reflected light from the interface between glass substrate...

Photochemical phase transition behavior of polymer azobenzene liquid crystals (LCs) was explored by transmission-mode analysis and reflection-mode analysis. Four samples with different structures were used, which show LC behavior in the trans form but no LC phase in the cis isomer. Attention was focused on the effect of the position of the mesogenic azobenzene moiety in the flexible side chain on the photochemical phase transition behavior. Photoirradiation of a thin film of the azobenzene LCs (∼200 nm) in the trans form resulted in the disappearance of the LC phase due to trans-cis photoisomerization of each mesogen. and the LC phase recovered quickly when the irradiated sample was kept in the dark because of thermal cis-trans back-isomerization. In all polymers, the photochemical LC to isotropic (I) phase transition was induced in 100∼200 us on laser pulse irradiation. In the sample with an azobenzene located apart from the main chain of the polymer by a spacer, the LC-I phase transition took p...

Fluorescence properties of azobenzene liquid crystal, 4,4′-dioctyloxy- azobenzene, were examined by steady-state and picosecond single-photon timing spectroscopy. It was found that the fluorescence from azobenzene aggregate with a peak at ∼ 630 nm was observed in the solid phase in addition to the very weak S2 fluorescence from azobenzene monomer centered at 420 nm. The fluorescence lifetimes of both aggregate and monomer S2 state were estimated to be approximately 150 ps and shorter than 2 ps. The relationship between the excited-state dynamics of azobenzene liquid crystal and its phase transition was analyzed on the basis of the temperature dependence of relative fluorescence intensity and fluorescence lifetime of aggregate.

Optical switching behavior of low-molecular-weight and polymer azobenzene liquid crystals (LCs) was explored by means of reflection-mode analysis. Reflectivity changed on pulse irradiation under va...

Progress for two or three decades in Pd complexpromoted alternating copolymerization of alkenes with carbon monoxide has enabled many polyketones to be synthesized with regulated structures and molecular weights.

Electroluminescent (EL) behavior has been evaluated in a cell which contained molecular dispersion of 1,4-bis(N,N-diphenylaminophenyl-1,3,4-oxadiazolyl)benzene (OXD) in a low-molecularweight liquid crystal, 4-octyloxy-4′-cyanobiphenyl (8OCB). EL emission was observed above the temperature where the OXD/8OCB mixture showed a liquid-crystalline phase. Furthermore, we fabricated an EL device which consisted of interdigital electrodes coated onto a glass substrate. It was found that the EL emission from the device was highly polarized.