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Photonic shape memory (SM) polymers based on liquid crystalline blue phase (BP) films have been fabricated by self-assembly and subsequent photopolymerization of liquid-crystal mixtures. These freestanding BP films exhibit narrow photonic band gaps and high reflectivity in the visible wavelength range. Multiple blue-shift colors are achieved by SM programming process at different mechanical pressures. The blue-shift colors can be attributed to a decrease of effective BP pitch along the viewing direction caused by the compressed deformation of the BP films, which are confirmed by a three-dimensional interometric profile. The deformed BP films can recover to their original shapes and reflecting colors by heating the polymer films to temperatures above the glass-transition temperature. Quantitative relationships between the shape change and optical response are established for understanding this SM effect. What is more, the temporary photonic patterns can be reversibly written and erased for dozens of cycles without apparent degradation, making these freestanding BP films appealing as rewritable photonic papers and optical sensors.

Fabrication of liquid-crystalline polymer networks with periodic nanoscale features is highly desired for photonic applications. Here, a printable photonic polymer coating has been fabricated from a monodomain liquid crystalline blue phase (BP) network. The BP polymer coating with high reflectivity is covalently linked to the glass substrate, which can be patterned by using an LC-ink to swell the network. The degree of swelling depends on the printed amount of LC-ink which can be controlled through adjusting the voltages of the inkjet printer. Arbitrary multicolour patterns covering the visible spectrum from 451 to 618 nm can be printed and erased multiple times, making these BP polymer coatings promising as rewritable photonic papers and responsive photonic materials.

Crosslinked liquid-crystalline polymers (CLCPs) containing photochromic moieties show macroscopic deformation upon irradiation with light. This conversion of light energy into mechanical work is attributed to photosynergetic amplification of changes at multiscale: from nano to macro. This chapter focuses on recent progress of photomobile polymer materials to achieve versatile design as soft actuators. Three approaches are detailed: incorporation of amorphous polymers into CLCPs to control mechanical and photoresponsive properties, reshaping of CLCPs into various three-dimensional architectures through the rearrangement of network structures, and application of two-photon absorption processes to enhance the spatial selectivity of photoactuation.

We prepared crosslinked azobenzene main-chain liquid-crystalline polymers (MCLCPs), in which the exchange of crosslinks can be brought about by transesterification reactions. The exchangeab...

We prepared 2 types of crosslinked liquid-crystalline polymers (CLCPs) (polyacrylates) with the same side-chain length but a different position of an azobenzene moiety in the side chain. We...

Poly(4-vinylpyridine) (P4VP) brushes were grafted onto a substrate via Cu(0)-mediated atom transfer radical polymerization and 1-pyrenebutyric acid (PBA) was incorporated into the brushes t...

Composite systems of liquid crystals (LCs) and polymers have been extensively studied in various forms such as polymer-dispersed LCs and polymer-stabilised LCs. Blending LCs and polymers is an effective approach to design functional materials with stimuli responsiveness and durability. Here, we show the development of a novel composite material with crosslinked azobenzene LC polymer (PAzo) and poly(dimethylsiloxane) (PDMS) aiming at the improvement of photomobile polymer materials in mechanical properties. The composite films were prepared by photopolymerisation of azobenzene monomers in PDMS elastomers. By forming phase separated structure, in which PAzo chains were dispersed in PDMS matrix, fracture strain of photomobile polymer materials was significantly enhanced. The composite film showed macroscopic bending upon irradiation with UV light. This result implies that PAzo domains in polymer matrix can work as microactuators to afford macroscopic deformation of the whole film. The further improve...

Crosslinked liquid-crystalline polymers (CLCPs) containing azobenzene moieties show reversible macroscopic deformation upon irradiation with light. The deformation of CLCPs strongly depends on alig...

We prepared crosslinked azotolane liquid-crystalline polymer (LCP) films doped with a stilbene derivative (two-photon chromophore) utilizing an interpenetrating polymer network (IPN) structure. The IPN films bend toward the light source upon irradiation with femtosecond laser pulses at 600 nm, which can excite the stilbene derivative by two-photon absorption. The bending speed of the IPN films increases with the square of the laser pulse intensity, which is compelling evidence for the two-photon processes.

The chemical functionalization of nano-carbon materials such as single-walled carbon nanotubes (SWNTs) and graphene by metal complexes has attracted much attention due to the multitude of potential applications in efficient energy-conversion and -storage devices. The solubilization and single-chirality separation of SWNTs by surface modifications is a useful approach to manipulate SWNTs in the liquid phase. In this study, several Ru and Fe complexes containing two terminal quadruple hydrogen-bonded (H-bonded) ureidopyrimidinedione (UPy) groups were synthesized (Ru-1, Ru-UPy, and Fe-UPy) to form H-bonded supramolecular polymers by self-association. In order to control the solubility of these complexes in nonpolar solvents, Ru-UPy and Fe-UPy were endowed with long alkyl side chain groups in the coordinated 2,6-bis(benzimidazol-2-yl)pyridine ligand, while Ru-1 and Ru-2 do not contain such long alkyl chain groups. AFM measurements revealed that Ru-1, Ru-UPy, and Fe-UPy form a fiber-like network morphology on HOPG surfaces, arising from the H-bonded aggregation. However, only Ru-UPy and Fe-UPy are able to solubilize SWNTs effectively upon simple sonication in chlorobenzene. After the solubilization of a CoMoCAT® SWNT in chlorobenzene using Ru-UPy or Fe-UPy, UV-Vis-NIR spectra showed sharp peaks at 996 and 1150 nm, which were attributed to (6, 5) and (7, 6)-SWNTs. The Raman spectra of the solubilized SWNTs revealed peaks that were attributed to the radial breathing mode (RBM), which suggests an enrichment of semiconducting SWNTs, i.e., Ru-UPy and Fe-UPy are able to selectively solubilize semiconducting SWNTs. Cyclic voltammograms of films of SWNTs covered with Ru-UPy or Fe-UPy on ITO electrodes showed a well-defined adsorbed Ru(ii/iii) or Fe(ii/iii) wave. Upon addition of acid, the redox response from the adsorbed H-bonded Ru-UPy and Fe-UPy disappeared and only SWNTs were left on the ITO electrode. Moreover, the Ru-UPy/SWNT and Fe-UPy/SWNT hybrids exhibited non-linear I-V characteristics.

We developed photomobile polymer materials with interpenetrating polymer network (IPN) structures composed of crosslinked liquid-crystalline azobenzene polymer (PAzo) and poly(dimethylsiloxane) (PDMS). By introducing PDMS into a PAzo template network, IPN was formed without disturbing the alignment of mesogens in the PAzo network. The films showed macroscopic bending behavior upon irradiation with UV and visible light. Although the IPN film showed a phase separated structure, the bending speed was significantly enhanced compared with the pristine film of PAzo, thanks to the soft nature of PDMS. The present method of preparing IPNs can be a promising approach to combine PAzo with various polymers and enhance the mechanical and photoresponsive properties.

We have synthesized a photo-crosslinkable polythiophene copolymer functionalized with a cinnamate moiety to improve the stability of organic photovoltaic (OPV) cells. The active layer of OPV cells is generally bulk heterojunction (BHJ) that consists of two or more organic semiconductors. When BHJ forms a micro-phase-separated structure with a blend of two organic materials, its structure inclines to change into a macro-phase-separated one after some time. To stabilize the BHJ morphology, we used a crosslinkable polymer containing a cinnamate moiety. The copolymer film became insoluble after UV irradiation because of [2+2] dimerization of the cinnamate groups.

We synthesized polymers containing a liquid-crystalline (LC) oligothiophene moiety in the side chain. This oligothiophene shows LC behavior between 101°C and 194°C in its original form, while when incorporated into the side chains of a polymer, the resultant polymer showed a nematic phase in a much wider temperature range. Thin films of these polymers showed nano-phase-separated structures with domain sizes of 15–40 nm upon annealing.

Crosslinked liquid-crystalline polymers (CLCPs) show unique behavior of deforming macroscopically when stimulated with heat, electricity and light. However, they cannot be remolded and reshaped once prepared. Here, we designed crosslinked polysiloxane with side chain mesogens that contain exchangeable crosslinking points based on transesterification between phenyl benzoates and hydroxy groups. After the formation of a polymer network, a base catalyst was introduced into the CLCP. When heated at 80°C, a piece of the CLCP was reshaped into a film and separate pieces of the CLCP were fused together, indicating that the CLCP is remoldable.

We developed interpenetrating polymer networks (IPNs) composed of a crosslinked azobenzene liquid-crystalline polymer (PAzo) and poly(alkyl methacrylate)s (PAMAs). When irradiated with UV and visible light, the IPN films showed reversible bending. The photoresponsive and mechanical properties of PAzo films were significantly enhanced by incorporation of the PAMA components.

We prepared photomobile polymer materials composed of crosslinked azobenzene liquid-crystalline polymers (LCPs) and methacrylates with interpenetrating polymer network (IPN) structures, and explored their photoresponsive behavior. The IPN films exhibited reversible bending upon photoirradiation. In addition, the durability of the IPN films was much higher than that of the pristine crosslinked azobenzene LCP films.

Various fabrication methods of photomobile polymer materials containing photochromic moieties have been developed to improve their photoresponsive and mechanical properties. Here, we newly prepared photomobile polymer materials with interpenetrating polymer network (IPN) structures. The IPN films, which are composed of azobenzene liquid crystalline polymer (LCP) and polymethacrylates, showed reversible bending behavior upon exposure to UV and visible light. Bending speed of the IPN films became higher with decreasing glass-transition temperature of polymethacrylate components. The IPN film containing poly(dodecyl methacrylate) showed faster bending than the pristine azobenzene LCP film.

Organic light-emitting diodes (OLEDs) based on conjugated polymers exhibiting polarized emission have attracted much attention because of their potential as backlights for conventional liquid crystal (LC) displays and 3-D displays. We have reported a new series of LC polymers based on donor-acceptor architecture containing an oxadiazole (OXD) and several amine moieties in the same side chain, which exhibit bipolar character with a wide energy band gap. In this study, to develop phosphorescent OLEDs with polarized emission, we synthesized a platinum complex, Pt(4-decyloxy)salen, with emitting property, and fabricated the device consisting of Pt complex as a guest and LC polymers as a host material. The Pt complex exhibited high thermal stability, good solubility and an emission peak at 530 nm in dichloromethane. To obtain electroluminescense from the Pt complex, we fabricated ITO/rubbed PEDOT:PSS/Pt(4-decyloxy)salen:host polymer/MgAg devices. The devices emitted a yellowish green light, which was dominated...

Organic light-emitting diodes (OLEDs) based on chromophore-containing liquid crystals (LCs) can emit polarized light due to self-assembly of mesogenic chromophores. The stability of LC phases in LC polymers with a mesogenic group in the main chain is higher than that in the polymers containing a mesogenic group in the side chain. In this study, a novel family of polyesters containing a carbazole moiety as a hole-transporting unit and an oxadiazole (OXD) moiety as an electron-transporting unit in the main chain, P10-DOXDCz and P16-DOXDCz, were designed and synthesized. These polyesters were prepared by transesterification of N-hexyl-3,6-di[2-([1,3,4]oxadiazol-5-yl)-4-methylbenzoate]carbazole and 1,10-decanediol or 1,16-hexadecanediol at 220 °C for 20 h. They showed a nematic phase. Both P10-DOXDCz and P16-DOXDCz emitted intense blue fluorescence with a maximum at 439 nm and 450 nm in thin films, respectively, and their fluorescence quantum yields were 0.74 and 0.81 in solution, respectively. Both compounds...

We present a simple way to control the photoinduced bending direction of azobenzene-containing cross-linked liquid-crystalline polymers. By changing the location of the photoactive azobenzene moieties from cross-links to side-chains, the bending direction of the sample is reversed under identical irradiation conditions. In addition to providing a versatile route toward directionality control of the photoinduced macroscopic motions, this observation highlights the complicated nature of the photomechanical response of azobenzene-containing cross-linked liquid-crystalline polymers, showing that the photomobile behavior can be determined by seemingly small details on the materials design.

A new class of polymer materials has been developed that can convert light energy directly into mechanical work, and show a variety of three-dimensional movements simply from exposure to light. These polymer materials can be fabricated into any shape and size using photolithographic methods and it is expected they will be developed for various applications. In this paper recent progress of this interesting class of polymer material is reviewed.

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.

Uniaxially aligned azobenzene liquid-crystalline polymers crosslinked by hydrogen bonding can deform in response to actinic light. The polymers can be precisely shaped due to high processability of hydrogen-bonded polymers. The mechanical properties of the polymer fibers were improved by introducing single-walled carbon nanotubes as a filler material. Because of weak hydrogen bonding, starting materials can be recovered, reused and recycled, which is very useful in view of chemical resource utilization.

We proposed a new approach to fabricate bilayer films with a crosslinked azobenzene liquid-crystalline (LC) polymer. The polyethylene (PE) substrates were coated with linear azobenzene LC polymers, and then the azobenzene layers were crosslinked by irradiation with electron beams (EBs). In the EB-irradiated films with ordered azobenzene moieties, exposure to UV light caused trans-cis isomerization and the change in alignment of azobenzene moieties. Bending of the bilayer films could be induced toward an actinic light source when they were irradiated from the side of the azobenzene layer, while they bent away from the actinic light source upon UV irradiation from the side of the PE layer. In both cases, the bent films reverted to the initial flat state by turning off the light, which could be repeated at room temperature.

A telechelic poly(N-isopropylacrylamide) (PNIPAM) with azobenzene end-groups (telechelic Az-PNIPAM) was prepared by reversible addition-fragmentation chain transfer (RAFT) free radical polymerization of NIPAM. This polymer self-assembles in cold water forming nanoparticles with a hydrodynamic radius (R H) of 8 nm and an aggregation number of 29 chains. The thermoresponsive behavior of Az-PNIPAM in water was investigated by turbidimetry and light scattering. In addition, the photoresponsive behavior of aqueous Az-PNIPAM was investigated by monitoring the changes with temperature of the solution and transmittance at 650 nm before and after irradiation at 366 nm.

We studied the effects of concentration and location of azobenzene chromophores on the photoinduced deformation of crosslinked liquid-crystalline polymers (CLCPs). The concentration of azobenzene chromophores in CLCP affects the degree of isomerization of azobenzene moieties and the macroscopic deformation behaviour of the films while the location of azobenzene moieties determines the contraction force and length.

Blue-emitting polymers based on a donor-acceptor architecture composed of oxadiazole and carbazole moieties containing various substituted groups in the same side chain were used as a host polymer in phosphorescent polymer light-emitting diodes (PhPLEDs). The polymer containing N-methylcarbazole showed a liquid-crystalline (LC) phase above its glass transition temperature but the other polymer containing N-ethylhexylcarbazole exhibited an amorphous phase. The single-layer PLEDs using these polymers exhibited blue emission with peaks from 430 to 440 nm. To examine the LC polymer (LCP) and the amorphous polymer as host materials, we fabricated simple devices using Ir(ppy)3 and (btp)2lr(acac) as phosphorescent dopants at various doping concentrations. The device composed of lTO/PEDOT-PSS/2 wt% of (btp)2Ir(acac) doped into LCP/MgAg showed intense red light (0.67, 0.32) with the luminance efficiency of 4.7 cd/A. The luminance efficiency of the PhPLEDs using the LCP was higher than that of the PhPLEDs using the...

Two azobenzene-containing block copolymers with an oxyethylene (P1) or an alkyl (P2) spacer in the side chain were prepared by atom transfer radical polymerization (ATRP). Neither of the block copolymers with a low azobenzene content showed a liquid-crystalline phase. However, their glass transition temperatures (T gs) were lowered by introducing flexible spacers. In particular, T g was lowered by about 30°C in P1. Their photoalignment and holographic behavior was investigated at various temperatures in thin films. Rapid changes in refractive index were induced in the P1 films upon irradiation at a temperature below T g. But the photoinduced birefringence in the P1 film was lower than that in the P2 films. Similar results were obtained in holographic recording. The azobenzene-containing block copolymer with the oxyethylene spacer (P1) used in this study has potential application for dynamic hologram.

Laminated films composed of a flexible plastic sheet and a crosslinked azobenzene liquid-crystalline polymer (CLCP) layer with different initial alignment of azobenzene mesogens were prepared by thermal compression bonding of a CLCP film and an unstretched low-density polyethylene (PE) film with an adhesion layer. In both laminated films with a homogeneous alignment of mesogens and a homeotropic one, large movements could be induced by irradiation with UV light at room temperature. A partly laminated film with homogeneous CLCP bent from both ends of the whole film, while one with homeotropic CLCP bent up from the center of the film toward the light source. These results indicate that we enable plastic films with no photoresponsive property to move flexibly upon photoirradiation just by laminating the CLCP layers partly, and the photoinduced motions of the laminated films are completely dependent on the alignment direction of the mesogens in the CLCP layers. In addition, it was found that the maximum stres...

Plastic films coated with crosslinked liquid-crystalline polymer (CLCP) layers containing azobenzene moieties (plastic/CLCP bilayer films) were prepared by thermal polymerization of mixtures of an azobenzene monomer and a crosslinker placed between a plastic film and a glass substrate. When the glass substrate was untreated, the obtained bilayer film bent slightly away from the UV light source when irradiated on the CLCP layer side. This bending direction was the same as that of a hybridly aligned CLCP film. When the glass substrate was coated with a rubbed polyimide to strengthen the homogeneous alignment of the azobenzene moieties of the CLCP surface layer, the obtained bilayer film bent toward the irradiation direction of the incident UV light. It was the same as a homogeneously aligned CLCP film and the degree of bending was larger than that of the untreated sample. This means that the photoinduced bending behavior of the plastic/CLCP bilayer films strongly depends on the alignment of the azobenzene m...

Three azobenzene acrylate monomers containing alkyl spacers of different length were synthesized. Thermodynamic and mesomorphic properties of the monomers were measured by differential scanning calorimetry and polarizing optical microscopy. A crosslinker with the undecyl spacer was also synthesized to prepare crosslinked liquid-crystalline polymer films by photopolymerization. Polarized UV spectra and polarizing optical micrographs demonstrated that the mesogens are aligned homogeneously in the films. Low glass transition temperature of the films enabled them to bend near room temperature upon UV irradiation. Besides, the films generally bent away from the light source before they at last bent towards the light irradiation.

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-...

We studied the photo-induced dynamics in a LC polymer film including azobenzene by using a time-resolved and a microscopic technique. The film was confined in a liquid crystal cell, while it is a photomobile film under a free standing condition, which is triggered by the photoisomerization of azobenezene. From the result of the time-resolved measurements, the change inside the film induced by UV irradiation was highly anisotropic polarization change. Microscopic observation revealed that the film was consisted of ordered and disordered region with a patched structure, and the UV induced change was travelled in the ordered region on the order of seconds.

A novel nickel complex ligated with 2-(2,6-diisopropylanilino)-1,4-naphthoquinone (1) was synthesized. The molecular structure of 1 determined by X-ray analysis was a square-planar geometry. Complex 1 conducted ethylene polymerization at 40 °C in a low activity to give linear polyethylene. On the other hand, 1 activated with 4 eq. of B(C 6 F 5 ) 3 was highly active for ethylene polymerization and gave a polymer possessing short chain branches of methyl, ethyl and propyl groups formed by a chain walking mechanism, as well as long chain branches, of which the content was almost the same as the total content of short chain branches. These results suggest that the macromonomer formed via β-hydride elimination should have effectively copolymerized with ethylene to give the long chain branches in the B(C 6 F 5 ) 3 -activated system.

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.

Cross-linked liquid-crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross-linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross-linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed-ring to open-ring isomerization, the bent films revert to the initial flat state. Without visible-light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross-linked diarylethene LC polymers.

Liquid-crystalline polymers containing an oxadiazole moiety as an electron-transporting unit and a carbazole moiety as a hole-transporting unit in the same side chain were designed and synthesized to investigate electroluminescent (EL) properties. The synthesized polymers showed high fluorescence quantum efficiency. Furthermore, it was found that the luminescent polymers possessed bipolar carrier-transporting property. The single-layer organic light-emitting diode was fabricated to demonstrate EL emission. The device, ITO glass/the polymer/MgAg, exhibited intense blue emission with a maximum brightness of 30 cd/m2 at 30 V.

The change in transmittance of a 1.55-μm laser beam was investigated by a photochemical phase transition of an azobenzene liquid-crystalline polymer. Effects of the intensity of actinic light and temperature on the photoresponsive behavior were explored using laser beams at 633 nm and 1.55 μm. It was found that the intensity of the actinic light or temperature affected on the response, regardless of the wavelength of the probe beam.

We have synthesized two types of azobenzene liquid-crystalline polymers with a tolane moiety exhibiting high birefringence: one is the copolymer having an azobenzene moiety and a 3-ring tolane group in the side chain (PA-3T) and the other is the polymer containing a long mesogen core, in which the azobenzene group is directly connected to the tolane moiety (P3AT). The values of 0.35 and 0.39 in birefringence were obtained in PA-3T and P3AT, respectively. When the film was irradiated with a writing beam at 488 nm, the change in birefringence was efficiently induced with P3AT compared with PA-3T.

Starting in the 1960s, several kinds of photodeformable polymers have been developed, such as monolayers, polymer gels, solid films and liquid-crystalline elastomers with different photodeformation mechanisms. This field evolved slowly until recently when significant achievements have been made. Most recently, Lendlein and co-workers have put forward another new concept - using photo-crosslinking to prepare deformable polymers with various pre-determined shapes (Nature 2005, 434, 879). This highlight gives a general introduction into photodeformable polymers and brings forth future challenges.

[t-BuNSiMe2(2,7-t-Bu2Flu)]TiMe2 and [t-BuNSiMe2(3,6-t-Bu2Flu)]TiMe2 were synthesized and characterized by elemental analysis, 1H NMR, and single-crystal X-ray analysis. These complexes were applied for propylene polymerization using dried modified methyaluminoxane (dMMAO) as a cocatalyst at 0 and 25 °C. The introduction of tert-butyl substituents to the fluorenyl ligand improved the activity more than 3 times regardless of the position of the substituents. The postpolymerization testified that both catalytic systems conducted the propylene polymerization in a living manner at both 0 and 25 °C. The propagation rate increased linearly against the Al/Ti ratio from the range of 100−400 with keeping the number of polymer chains constant, which directly indicates that a larger amount of dMMAO enhanced the propagation rate. The introduction of tert-butyl substituents also improved the syndiospecificity: the 3,6-position was more effective than the 2,7-position, and [t-BuNSiMe2(3,6-t-Bu2Flu)]TiMe2 gave the livin...

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.

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.

Oriented liquid-crystalline network films with various cross-linking densities were prepared by polymerization of mixtures of mono- and diacrylates, both of which contain azobenzene chromophores. The optical anisotropy in the films was evaluated by polarizing optical microscopy and polarized IR spectroscopy. The dichroic ratios and the order parameters of the films were estimated from polarized UV absorbance. The free-standing films were found to show photoinduced bending and unbending behavior upon alternate exposure to unpolarized UV light at 366 nm and unpolarized visible light at >540 nm. It was observed that the films with different cross-linking densities exhibited different bending extents and speeds.