Nobuhiro Kawatsuki

We report a strategy for tuning birefringence in photoalignable liquid-crystalline copolymer (PLCP) films through in situ modification of mesogenic side groups. A PLCP containing 4-formylphenyl benzoate (PA) and cinnamic acid (CA) units was reacted with five phenylamine derivatives after axis-selective photoreactions induced by linearly polarized light. The condensation sequence and phenylamine structure strongly affected molecular reorientation and birefringence development. Microwave-assisted processing enabled rapid condensation and simultaneous molecular reorganization, yielding a maximum birefringence of Δn = 0.47 at 527 nm for 2-aminofluorene (AF)-modified films. Thick (∼2000 nm) AF-modified PLCP films exhibited high transparency and retardation values up to 625 nm and were further applied to highly efficient near-infrared polarization gratings operating at 1550 nm with diffraction efficiencies of 86–87%. These results demonstrate that in situ mesogenic modification provides an effective route to highly birefringent PLCP films for photonic applications.

Mechanochromism is a phenomenon in which mechanical stimuli change the optical properties of a material, such as its color and emission properties. Various materials exhibiting this behavior have been intensively studied. Mechanochromic materials that exploit liquid crystals have been previously reported. Using liquid crystals, properties different from those of conventional materials, such as anisotropic response and multicolored luminescence due to intermediate aggregation phase stabilization, can be expected. Recently, we reported the preparation and evaluation of the optical properties of liquid-crystalline mechanochromic dyes with cholesterol terminals. The dyes formed gels in some solvents, changed their emission color, and exhibited a friable response without reaching a crystalline state. In addition, film-forming properties, processability, and responsiveness were improved in thin films mixed with polymers. However, the mechanical and thermal stabilities of the gels were low. In this study, a compound similar to the polymerizable unit was synthesized to produce tougher gels. In addition, triblock polymers with a mechanoresponsive dye in the hard segment were synthesized. The xerogel film prepared from the monomer showed an irreversible blue shift in photoluminescent color by mechanical grinding and also exhibited linearly polarized photoluminescence by uniaxial grinding due to force-induced alignment. On the other hand, the xerogel film prepared from the triblock copolymer showed a blue shift in photoluminescent color that can approximately revert to the initial state by thermal annealing, though it showed no anisotropy by uniaxial grinding, indicating that polymerization partially preserves mechanical responsiveness.

Controlling the birefringence of optical films is imperative to fabricate thin birefringent optical devices. Here, new photoalignable liquid crystalline copolymers (PLCPs) with 4-formylphneyl benzoate (PA) and cinnamic acid (CA) side groups are synthesized, which attain high photoreactivity and controllability of the orientation direction. Additionally, the exposed films are treated with 2-aminofluorene (AF) for an in situ condensation of PA with AF to form a Schiff base with a high inherent birefringence. Birefringence of the photoaligned film can be controlled up to 0.45 without disturbing the photoinduced orientation structure.

In this study, we describe the synthesis of a cholesterol-linked cyanostilobazole salt dye and the tuning of its luminescence by physical stimuli such as electricity and grinding. The dyes exhibited liquid-crystalline properties at temperatures above 170 °C. Some of the solutions were transformed into orange luminescent gels upon the addition of poor solvents. When the solvent was evaporated, the resulting solid xerogel exhibited mechanochromism, its color changed, and its luminescent color changed from orange to red. Furthermore, we investigated the construction of functional gels (mechanochromic gels) that can respond to two stimuli, damage detection by abrasive responsiveness, and electrical response using ionic liquid complexes of polymers as dispersing media. This study provides a new strategy for tuning and switching luminescence using non-chemical stimuli in a single-component system using aggregation.

Copolymer films of photoalignable liquid crystalline (LC) copolymethacrylates comprised of a phenyl benzoate mesogen connected with N-benzylideneaniline end moiety (NBA2) and benzoic acid (BA) side groups exhibit a photoinduced reorientation behavior. Significant thermally stimulated molecular reorientation attains a dichroism (D) greater than 0.7 for all copolymer films and a birefringence of 0.113–0.181. In situ thermal hydrolysis of the oriented NBA2 groups decreases the birefringence to 0.111–0.128. However, the oriented structures of the film are maintained, demonstrating a photo-durability, even though the NBA2 side groups photo-react. The hydrolyzed oriented films show higher photo-durability without changing their optical properties.

An optical system consisting of a straight-line polarization grating (SPG) and two parabolic-line polarization gratings (PPGs) is presented for the characterization of optical vortices (OVs) with arbitrary states of polarization (SoPs). The PPG is capable of converting an OV with a specific SoP into a bright bar-like spot with 100% efficiency. The number of dark lines and their orientation respectively correspond to the magnitude and sign of topological charge (TC) of the incident OV, thereby enabling characterization of OVs with high efficiency. Furthermore, on combining an SPG with PPGs, the present system can characterize the TC of incident OVs regardless of their SoP. The feasibility of the system was demonstrated in experiments using gratings fabricated by applying the photoalignment method and employing films of a photo-crosslinkable polymer liquid crystal. The experimentally obtained efficiency is 70.2%. We furthermore demonstrate the system’s capability to characterize polarization vortices.

Thermally stimulated photoinduced reorientation of liquid crystalline (LC) polymethacrylate composed of a phenyl benzoate mesogen connected with N-benzylideneaniline (NBA2) end moiety exhibits a significant molecular reorientation (D > 0.7) when the film is exposed to linearly polarized 313 nm light and subsequently annealed in the LC temperature range of the material. Hydrolysis of the NBA2 end moieties yields an oriented mesogen with phenylamine moieties without distorting the oriented structure. In situ condensation of 2-hydroxybenzaldehyde derivatives and phenylamine moieties yields oriented N-salicylideneaniline side groups. The resultant film displays a polarized fluorescence with a polarization ratio up to 3.4.

Polarized fluorescence of oriented N-salicylideneaniline (SA) derivatives is explored based on the thermally stimulated photoinduced molecular reorientation of liquid crystalline (LC) copolymethacrylate with N-benzylideneaniline derivative (NBA2) and benzoic acid (BA) side groups. The LC copolymer films show significant cooperative molecular reorientation of the NBA2 and BA side groups (D > 0.7). Subsequent thermal hydrolysis of the NBA2 side groups yields free phenylamine moieties. These moieties can form oriented SA derivatives via in situ condensation with 2-hydroxybenzaldehyde derivatives. The excited-state intermolecular proton transfer of the oriented SA molecules induces polarized fluorescence at 510–548 nm with a polarization ratio up to 6.2. Direct in situ exchange from the oriented NBA2 to SA derivatives achieves polarized fluorescence similar to that of the SA side groups.

Photoresponsive photoalignable liquid crystalline polymers composed of phenyl benzoate terminated with N-benzylideneaniline were evaluated. These polymers are capable of axis-selective photoreaction, photoinduced orientation, and surface relief grating formation. Polarization holography using an He-Cd laser beam at a wavelength of 325 nm demonstrated the formation of a surface relief grating with a molecularly oriented structure based on periodic light-induced reorientation and molecular motion. Electrical switching of diffracted light using an electric field response of twisted-nematic cell containing a low-molecular-weight liquid crystal in combination was also demonstrated.