Photochromic chiral liquid crystalline systems containing spiro-oxazine with a chiral substituent I. Synthesis and characterization of compounds

Photochromic acrylates containing both biphenylene and spiro-oxazine moieties with a chiral substituent and the related polymers were prepared and yielded photochromic chiral liquid crystalline systems. The photochromic acrylates containing both an undecamethylene group and a (2S, 3S)-2-chloro-3-methylpentanoyloxy group (A11SOP) or a (-)-menthoxyacetoxy group (A11SOM) gave a supercooled mesophase; the latter reflected right-handed visible light (blue colour) at room temperature. On the other hand, the photochromic acrylate containing both the (R)-(-)-2-methylpropylene and (2S, 3S)-2-chloro-3-methylpentanoyloxy groups (A3SOP) showed no mesophase. The related homopolymers, PA11SOP and PA11SOM, did not exhibit mesophases because of steric hindrance between the side groups of the polymers. However, only PA11SOM exhibited shear-induced birefringence under 100-104°C. Several copolymers consisting of the nematogenic monomer, 4-[4-(6-acryloyloxyhexyloxy)benzoyloxy]benzonitrile (A6CN), and A11SOP or A11SOM possessed a smectic phase due to reduction of the steric hindrance between the potentially smectogenic A11SOP or A11SOM moieties.     

Alignment of liquid crystals induced by a photopolymerized self‐assembled film

An alignment film derived from a photopolymerized self‐assembled film may be used to orient nematic liquid crystals after irradiating the film with linearly polarized UV (LPUV). A photosensitive cationic amphiphile was first synthesized containing two double bonds and which could be polymerized by UV. A layer‐by‐layer self‐assembled multilayer film was next prepared in an aqueous solution of the cationic amphiphile and poly(sodium 4‐styrenesulphonate); the UV‐Vis spectra showed that each layer of the LBL multilayer film was uniform. When the film was irradiated by LPUV, the photosensitive double bonds underwent [2+2] cycloaddition along the vector direction of LPUV. The polarized UV‐Vis absorption spectra also provided evidence that the film was anisotropic, i.e. the photopolymerization was along a certain direction. The anisotropic film was used as an alignment layer for nematic liquid crystals, and observations under a polarizing microscope indicated that the alignment of the liquid crystals was good, as expected, and that the orientation direction of the liquid crystals was always perpendicular to the electric vector of the irradiating LPUV.     

Synthesis of terminally substituted stilbene-tolane liquid crystals

Methods for synthesizing substituted alkyl and fluoro stilbene-tolane (PTPDP) liquid crystal materials are presented. These compounds show a slightly higher birefringence than the analogous bistolanes, but higher melting points and heats of fusion. Potential applications of these compounds for optical communications and displays are discussed.     

Optical properties of a mesogen by image analysis

An image analysis technique in conjunction with polarising optical microscopy (POM) is proposed for assessment of the thermo-optical properties of homogeneously aligned chiral ester liquid crystals of the type ((S)-(-)-2-methylbutyl 4′-(4″-n-alkanoyloxybenzoyloxy) biphenyl-4-carboxylates, where n?=?16 or 18. Chiral ester textures are recorded as a function of temperature using POM provided with a hot-stage and a high-resolution colour camera. Temperature-dependent optical parameters, or thermo-optical properties such as optical transmission, degree of polarisation, absorption coefficient and birefringence are computed for chiral esters by analysing the texture of samples using MATLAB software. This is a simple experimental technique for observing how the optical parameters of liquid crystals change with temperature.     

Software package SIMPRE—Revisited

This article elucidates the pitfalls identified in the software package SIMPRE recently developed by Baldoví et al. (J. Comput. Chem. 2013, 34, 1961) for modeling the spectroscopic and magnetic properties of single ion magnets as well as single‐molecule magnets. Analysis of the methodology used therein reveals that the crystal field parameters (CFPs), expressed nominally in the Stevens formalism, exhibit features characteristic for the CFPs expressed in the Wybourne notation. The resemblance of the two types of CFPs introduces a serious confusion that may lead to wrong comparisons of the CFPs taken from various sources. To clarify this confusion, the properties of the CFPs ( , ) associated with the Stevens operators ( X = S , J , or L ), which belong to the class of the tesseral‐tensor operators, are contrasted with those of the CFPs B_kq associated with the Wybourne operators , which belong to the class of the spherical‐tensor operators. Importantly, the confused properties of Stevens and Wybourne operators may bear on reliability of SIMPRE calculations. To consider this question independent calculations are carried out using the complete approach and compared with those of the restricted approach utilized earlier. It appears that the numerical results of the package SIMPRE are formally acceptable, however, the meaning of the CFPs must be properly reformulated. Several other conceptual problems arising from misinterpretations of the crucial notions and the CFP notations identified therein are also discussed and clarified. © 2014 Wiley Periodicals, Inc.     

Spin and orbital magnetic moments and spin anisotropy energies of light rare earth atoms embedded in graphene: A first-principles study

The geometries, electronic structures, spin magnetic moments (SMMs), orbital magnetic moments (OMMs) and spin anisotropy energies (SAEs) of light rare earth atoms (La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) embedded in graphene were studied by using first-principles calculations based on Density Functional Theory (DFT). The spin-orbital coupling effect was taken into account and GGA+U method was adopted to describe the strongly localized and correlated 4f electrons. There is a significant deformation of the graphene plane after doping and optimization. The deformation of Gd doped graphene is the largest, while Eu the smallest. The results show that the valence is +3 for La, Ce, Pr, Nd, Pm, Sm and Gd, and +2 for Eu. Except Eu and Gd, there are obvious OMMs. When the spin is in the Z direction, the OMMs are −0.941 μ_B, −1.663 μ_B, −3.239 μ_B, −3.276 μ_B and −3.337 μ_B for Ce, Pr, Nd, Pm and Sm, respectively, and point the opposite direction of SMMs. All the doped systems except Gd show considerable SAEs. For Ce, Pr, Nd, Pm, Sm, and Eu, the SAEs are −0.928 meV, 20.941 meV, −8.848 meV, 7.855 meV, 75.070 meV and 0.810 meV, respectively. When the spin orientation is different, different orbital angular moments lead to apparent charge density difference of the 4f atoms, which can also explain the origin of SAEs.     

消除7A05铝合金板材各向异性的热处理工艺

为提高7A05铝合金热轧板材的综合力学性能并减少各向异性,对7A05铝合金固溶、预时效、时效和形变处理等工艺对性能的影响进行了系统的研究. 比较了供货态、形变态、回归(RRA)态和采用预时效形变热处理的优化态热处理工艺对综合力学性能的影响. 结果表明:固溶的最佳温度为480 ℃,单级时效最佳工艺为120 ℃,24 h,双级时效中第一级时效最佳工艺为90 ℃,8 h,最佳形变为25%. 通过金相组织和力学性能测试结果表明:由于预时效析出促进形变热处理时亚晶等轴化,优化态强度高,进一步改善了合金性能,减少了轧制板材纵横向力学性能各向异性倾向.     

A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.