Exploring the Impact of Linkage Structure in Ferroelectric Nematic and Smectic Liquid Crystals.

The liquid crystal molecule 3-fluoro-4-(3,4,5-trifluorophenyl)phenyl 2,6-difluoro-4-(trans-5-n-propyl-1,3-dioxane-2-yl)benzoate (DIO) has attracted considerable interest owing to its unique ferroelectric nematic phase and extraordinarily high dielectric constant. To expand the DIO series, novel analogs with 1,3-dioxane units converted to ester units (EST analogs) were synthesized, and their physical properties were characterized. The EST analogs exhibited ferroelectric phases similar to those of the corresponding DIO analogs. Interestingly, an EST analogue featuring a defluorinated benzoate unit exhibited a ferroelectric smectic A phase, despite its smaller longitudinal dipole moment of 6.9 D. This result diverges from the common knowledge that the formation of large longitudinal dipoles is traditionally effective in the emergence of ferroelectric phases. Unlike the DIO series, the EST analogs can be readily obtained without the formation of undesired geometric isomers, which is advantageous for practical applications. The results of this study provide valuable insights into the design of liquid-crystalline materials expressing ferroelectric phases.

Fluid Layered Ferroelectrics with Global C∞v Symmetry.

Ferroelectricity in fluid materials, which allows free rotation of molecules, is an unusual phenomenon raising cutting-edge questions in science. Conventional ferroelectric liquid crystals have been found in phases with low symmetry that permit the presence of spontaneous polarization. Recently, the discovery of ferroelectricity with high symmetry in the nematic phase has attracted considerable attention. However, the physical mechanism and molecular origin of ferroelectricity are poorly understood and a large domain of macroscopically oriented spontaneous polarization is difficult to fabricate in the ferroelectric nematic phase. This study reports new fluid layered ferroelectrics with the C∞v symmetry in which nearly complete orientation of the spontaneous polarization remains stable under zero electric field without any orientation treatment. These ferroelectrics are obtained by simplifying the molecular structure of a compound with a known ferroelectric nematic phase, although the simplification reduced the dipole moment. The results provide useful insights into the mechanism of ferroelectricity due to dipole-dipole interactions in molecular assemblies. The new ferroelectric materials are promising for a wide range of applications as soft ferroelectrics.

Reworkable Polyhydroxyurethane Films with Reversible Acetal Networks Obtained from Multifunctional Six-Membered Cyclic Carbonates.

Multifunctional 6-membered cyclic carbonates (6-CCs) comprising acetal structures have been synthesized via phosgene-free routes and utilized for the fabrication of reworkable networked poly(acetal-hydroxyurethane) (PAHU) films. Dibenzoyl-protected di(trimethylolpropane) (DTMP) reacts with multifunctional aldehydes derived from nonexpensive alcohols to afford protected multifunctional DTMPs. After deprotection, the multifunctional DTMPs can react with diphenyl carbonate to efficiently form multifunctional 6-CCs. The polyaddition of the 6-CCs and diamines effectively proceeds in DMF to give networked PAHU films with good transparency and flexibility. These films possess the reworkability based on acid-catalyzed reversibility of acetal linkages. In particular, the film fabricated using large amounts of hexa-functional 6-CCs can reform reproducibly with maintaining to some degree its mechanical properties.

Convenient chirality transfer from organics to titania: construction and optical properties.

Polyethyleneimine (PEI) complexed with chiral d- (or l-) tartaric acid (tart) in water can self-organize into chiral and crystalline PEI/tart assemblies. It has been previously confirmed that the complexes of PEI/tart could work as catalytic/chiral templates to induce the deposition of SiO2 nanofibres with optical activity but without outwards shape chirality such as helices. In this work, we found that the templating functions of PEI/tart were still effective to prompt the deposition of TiO2 to form chiral PEI/tart@TiO2 hybrid nanofibres under aqueous and room temperature conditions within two hours. Furthermore, the co-deposition of TiO2 and SiO2 was also fulfilled to yield chiral PEI/tart@TiO2/SiO2 nanofibres. These TiO2-containing hybrid nanofibres showed non-helical shapes on the length scale; however, chiroptical signals with mirror relation around the UV-Vis absorption band of TiO2 remarkably appeared on their circular dichroism (CD) spectra. By means of the protocols of XRD, TEM, SEM, UV-Vis, CD and XPS, structural features and thermoproperties of the chiral TiO2 and SiO2/TiO2 were investigated.

Nanosheet-stacked chiral silica transcribed from metal ion- and pH-tuned supramolecular crystalline complexes of polyamine-D-glucarate.

D-glucaric acid (D-Glc) associates with linear poly(ethyleneimine) (PEI) through hydrogen bonding and electrostatic interactions in aqueous media to form nanostructured crystalline PEI/D-Glc/H2O complexes with PEI/D-Glc/H2O ratios of 2:1:2. These complexes can serve as templates for silica depositions from hydrolytic condensation of tetramethoxysilane to guide morphologically duplicated silica under very mild conditions. Their microscale morphologies are tunable by use of the crystalline complexes regulated in the different pH of the PEI/D-Glc solutions. It was also found that some metal ions added in the PEI/D-Glc complexation process could have a synergistic effect under a certain pH regimes, bringing about remarkable changes in the hierarchy of the resulting complexes. Especially, the complexes formed through fine-tuning of the complexation conditions could direct torsionally stacked silica nanosheets, in which the nanosheets are composed of orderly-bundled nanofibrils. Final elimination of organic components of the templates afforded chiral inorganic silica while retaining the morphologically higher-order structures. The chirality of the silica, which was obtained after calcination at 600 °C, was characterized by means of diffused reflectance circular dichroism (DRCD) spectroscopy with a remote confirmation of the appearance of induced-CD (ICD) signals of achiral or racemic chromophores covalently linked on the silica frames. Interestingly, the shapes and signs of these ICD signals are dramatically changed depending on the pH-tuned templates used in silicification and are strongly correlated to that of the CD signals of the complex templates, indicating that the chiral transcription proceeds accurately with imprinting the higher-order chirality of the complexes on the morphologically structured silica networks.

Controlled formation of polyamine crystalline layers on glass surfaces and successive fabrication of hierarchically structured silica thin films.

The formation of silica films on the glass plate whose surface was precoated by crystalline linear poly(ethylenimine) (LPEI) in advance was systematically investigated via controlling the surface-specific crystallization of the LPEI on the glass plate. Immersing glass substrates into a hot aqueous solution of LPEI containing additives such as transition metal ions and acidic compounds and retaining them on 30 °C for desired periods resulted in the formation of crystalline LPEI layers on the substrates. Subsequently dipping this LPEI-coated glass into silica source solutions afforded successfully hierarchically structured silica film which coated continuously the surface of the substrates. In this two-step process, we found that the formation of hierarchically structured silica films strongly depended on the LPEI layer formed from the LPEI aqueous solutions containing different additives. The LPEI layer formed by changing the kinds of additives and their concentrations provides the differently structured silica films composed of turbine-like structures flatly lying-on and/or vertically standing-on as well as ribbon network structures on the surface of the substrates. Moreover, we functionalized these silica films by the introduction of hydrophobic alkyl chains or emissive Eu(III) complexes and investigated their wettability and emission properties.

Lipid-packaged linear iron(II) triazole complexes in solution: controlled spin conversion via solvophobic self-assembly.

Linear Fe(II) 1,2,4-triazole complexes with lipid counteranions are newly developed. These complexes show sharp and reversible spin conversion in toluene, with temperatures significantly higher (by 20-100 K) than the spin crossover temperatures observed in the crystalline states. This is accounted for in terms of increased metal-ligand interactions in organic media, which is caused by solvophobic compaction of charged coordination chains. In atomic force microscopy, developed nanowires are observed for low spin (LS) complexes. On the other hand, fragmented nanostructures are seen for high spin (HS) complexes, indicating that the spin conversion in solution is governed by a self-assembly process. The lipid packaging of charged coordination chains thus provides powerful means to improve and regulate their functions via solvophobic self-assembly.