Polarization holographic grating recording in the cholesteric azobenzene‐containing films with the phototunable helix pitch

The recording of polarization gratings in films of a cholesteric liquid crystalline polymer with different helix pitch was studied in detail. For this purpose, the cholesteric mixture of the nematic azobenzene‐containing copolymer with a chiral‐photochromic dopant was prepared. The utilization of such mixture has made possible to realize dual optical photorecording in one system, first due to the phototuning of the helix pitch by UV light and second the polarization grating recording process by exposure with polarized visible light. The diffraction efficiency strongly depends on the cholesteric helix pitch and films thickness: the increase of the confinement ratio d/p (where d, film thickness; p, helix pitch) results in growth of the diffraction efficiency. Comparison of the induction of polarization gratings in cholesteric, nematic (copolymer without chiral dopant), and amorphous (nonannealed) cholesteric films revealed that only the cholesteric films were characterized by significant oscillations in the diffraction efficiency signal as well as by the presence of the maximum in the first‐order diffraction efficiency in the initial stage of the grating recording process. It was found that in addition to the polarization grating surface relief gratings (SRGs) were also formed in the studied systems, however, the amplitude of the SRG inscribed in the cholesteric films was lower (～20 nm) compared to the grating amplitude obtained in nematic films (～60 nm). Moreover, increasing helix pitch resulted in a decrease of the SRG amplitude. The obtained experimental data demonstrate the great potential of cholesteric LC mixtures of such type for different applications as photoactive materials for photonics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 773–781     

Chirality sensing of chiral pyrrolidines and piperazines with a liquid crystalline dynamic helical poly(phenylacetylene) bearing ethyl phosphonate pendant groups

Stereoregular cis‐transoidal poly(phenylacetylene) bearing a phosphonic acid monoethyl ester as the pendant group (poly‐ 1 ‐H) was found to form a preferred‐handed helix upon complexation with various optically active pyrrolidines and piperazines in dilute dimethyl sulfoxide and water, and the complexes exhibited characteristic induced circular dichroisms (ICDs) in the UV‐vis region of the polymer backbone. The Cotton effect signs in water reflect the absolute configuration of the pyrrolidines. The sodium salt of poly‐ 1 ‐H (poly‐ 1 ‐Na) and poly‐ 1 ‐H in the presence of optically active amines formed lyotropic nematic and cholesteric liquid crystalline phases in concentrated water solutions, respectively, indicating the rigid‐rod characteristic of the polymer main chain regardless of the lack of a single‐handed helix, as evidenced by the long persistence length of about 18 nm before and after the preferred‐handed helicity induction in the polymer. X‐ray diffraction of the oriented films of the nematic and cholesteric liquid crystalline polymers exhibited almost the same diffraction pattern, suggesting that both polymers have the same helical structure; dynamically racemic and one‐handed helices, respectively. On the basis of the X‐ray analysis, a possible helical structure of poly‐ 1 is proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1383–1390, 2010     

Preparation and phase behavior of side‐chain cholesteric liquid‐crystalline elastomers

A series of new side‐chain cholesteric elastomers derived from cholesteryl 4‐(10‐undecylen‐1‐yloxy)‐4′‐ethoxybenzoate and phenyl 4,4′‐bis(10‐undecylen‐1‐yloxybenzoyloxy‐p‐ethoxybenzoate) was synthesized. The chemical structures of the monomers were confirmed by elemental analyses, Fourier transform infrared, and ¹H NMR and ¹³C NMR spectra. The mesomorphic properties of elastomers were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. Monomer M₁ showed a cholesteric phase, and M₂ displayed smectic and nematic phases. The elastomers containing <15 mol % of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3315–3323, 2005     

Effect of nematic ordering on the elasticity and yielding in disordered polymeric solids

The relation between elasticity and yielding is investigated in a model polymer solid by Molecular‐Dynamics simulations. By changing the bending stiffness of the chain and the bond length, semicrystalline and disordered glassy polymers — both with bond disorder — as well as nematic glassy polymers with bond ordering are obtained. It is found that in systems with bond disorder the ratio τ_Y/G between the shear yield strength τ_Y and the shear modulus G is close to the universal value of the atomic metallic glasses. The increase of the local nematic order in glasses leads to the increase of the shear modulus and the decrease of the shear yield strength, as observed in experiments on nematic thermosets. A tentative explanation of the subsequent reduction of the ratio τ_Y/G in terms of the distributions of the per‐monomer stress is offered. © 2017 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2017 , 55, 1760–1769     

Cholesteric mesophase of the hydrogen-bonded blends of liquid crystalline ionogenic copolymers with a low molecular weight chiral dopant

A family of a new hydrogen-bonded complexes based on comb-shaped LC copolymers containing the monomer units of cyanobiphenyl derivative and n-alkyloxy-4-oxybenzoic acid with a chiral dopant on the base of 4-pyridinecarboxylic acid and L -menthol, was prepared. At concentrations of chiral groups 1–25 mol %, the induction of cholesteric phase was observed. Temperature dependences of selective light reflection wavelengths were studied, and helix twisting power was calculated. Depending on the type of copolymer nematic matrix, this value is changed in the range from 12.1 to 19.6 µm⁻¹. It was shown that an increase of a distance between the chiral dopant and the main polymer chain results in a lower values of helix twisting power. With respect to optical properties, the chiral nematic phase in the hydrogen-bonded complexes is comparable to classical cholesteric copolymers, in which the chiral group is covalently bound to polymer chain. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3215–3225, 1999     

Comparison of structures and properties of lyotropic cholesteric phases induced by center and axial chiral compounds

We studied the phase chirality in disklike lyotropic cholesteric (Ch_D) phases which were obtained by adding center and axial chiral dopants to achiral lyotropic nematic (N_D) host phases. In a lyotropic nematic matrix of the N_D phase in the hexadecyldimethylethyl-ammonium bromide/water/n-decanol ternary system, a Ch_D phase was induced by adding center chiral sterols (cholesterol, prednisolon, taurocholic acid) and the axial optically active compound R(−)-1,1′- binaphthalene-2,2′-diyl-hydrogen phosphate (BDP). The helical twisting power (HTP) of BDP is generally lower than the HTP of inducing substances with center chirality, such as cholesterol, prednisolon, etc. At constant composition of the N_D phase, the helix lengths were determined from the ordered fingerprint texture, the so-called “spaghetti-like texture” seen in polarizing microscopy. The reciprocal helix lengths change linearly with the BDP concentration. The properties of the Ch_D phase (textures, helix lengths, micelle parameters) induced by the chiral compounds and changed by the composition of host phases give information on the mechanism of chirality transfer from the molecular level to that of the micellar aggregates and, eventually, to the liquid-crystalline superstructure. The structure in the Ch_D phase was described in the form of micelle parameters. For helix formation a minimum concentration of the chiral compounds is necessary. During the helix formation the number of micelles per helix length changes as a function of the concentration of the center and axial chiral molecules. The first step during the formation of the Ch_D phase is the solubilization of dopants into the micelles. Interaction between the optically active molecules then leads to the formation of hydrogen bridges between adjacent optically active molecules in the helical stack. Received: 20 December 1999/Accepted: 22 May 2000     

Synthesis and properties of mesogen‐jacketed liquid crystalline polymers containing bistolane mesogen

On the basis of the concept of mesogen‐jacketed liquid crystalline polymers, a series of new methacrylate monomers, (2,5‐bis[2‐(4′‐alkoxyphenyl) ethynyl] benzyl methacrylate (MACn, n = 4, 6, 8, 10, and 12) and 2,5‐bis[2‐(6′‐decanoxynaphthyl) ethynyl] benzyl methacrylate (MANC10), and their polymers, PMACn (n = 4, 6, 8, 10, and 12) and PMANC10 were synthesized. The bistolane mesogen with large π‐electron conjugation were side‐attached to the polymer backbone via short linkages. Various characterization techniques such as differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized light microscopy were used to study their mesomorphic phase behavior. The polymer PMACn with shorter flexible substituents (n = 4) forms the columnar nematic (?_N) phase, but other polymers with longer flexible tails (n = 6, 8, 10, and 12) can develop into a smetic A (S_A) phase instead of a ?_N phase. The PMANC10 containing naphthyl can also form a well‐defined S_A phase. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Double thermoresponsive block–random copolymers with adjustable phase transition temperatures: From block‐like to gradient‐like behavior

Stimuli‐responsive block–random copolymers are very useful “smart” materials as their switching behavior can be tuned by simply adjusting the composition of the random copolymer block. Because of that, we synthesized double thermoresponsive poly(N‐acryloylpyrrolidine)‐block‐poly(N‐acryloylpiperidine‐co‐N‐acryloylpyrrolidine) (PAPy‐b‐P(APi‐co‐APy)) copolymers via reversible addition fragmentation chain transfer (RAFT) polymerization and investigated their temperature‐induced self‐assembly in aqueous solution. By varying the APi/APy ratio in the random copolymer block, its phase transition temperature (PTT₁) can indeed be precisely adjusted while the temperature‐induced collapse upon heating leads to a fully reversible well‐defined micellization. By making the two blocks compositionally similar to more than 60%, the polymers' mechanistic thermoresponsiveness can furthermore be changed from block‐like to rather gradient‐like behavior. This means the micellization onset at PTT₁ and the corona collapse at the PTT of the more hydrophilic pure PAPy block (PTT₂) overlap resulting in one single broad transition. This work thus contributes to the detailed understanding of design, synthesis and mechanistic behavior of tailored “on‐demand” switchable materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 399–411     

Synthesis of laterally attached side‐chain liquid‐crystalline polynorbornenes with high mesogen density by ring‐opening metathesis polymerization

(±)‐exo,endo‐5,6‐Bis{[[11′‐[2″,5″‐bis[2‐(3′‐fluoro‐4′‐n‐alkoxyphenyl)ethynyl]phenyl]undecyl]oxy]carbonyl}bicyclo[2.2.1]hept‐2‐ene (n = 1–12) monomers were polymerized by ring‐opening metathesis polymerization in tetrahydrofuran at room temperature with Mo(CHCMe₂Ph)(N‐2,6‐ⁱPr₂Ph)(O^tBu)₂ as the initiator to produce polymers with number‐average degrees of polymerization of 8–37 and relatively narrow polydispersities (polydispersity index = 1.08–1.31). The thermotropic behavior of these materials was independent of the molecular weight and therefore representative of that of a polymer at approximately 15 repeat units. The polymers exhibited an enantiotropic nematic mesophase when n was 2 or greater. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4076–4087, 2006     

A Liquid Crystalline Oligomer Exhibiting Nematic and Twist‐Bend Nematic Mesophases

The twist‐bend nematic phase (N_TB) has been described as the structural link between the untilted uniaxial nematic phase (N) and the helical chiral nematic phase (N*). The N_TB phase exhibits phenomena of fundamental importance to science, that is, 1) the spontaneous formation of a helical pitch on the nanometer scale in a fluid and 2) the spontaneous breaking of mirror symmetry, leading to the emergence of chiral domains in an achiral system. In this Communication, we present a study on T4₉ [bis(4‐(9‐(4‐((4‐cyanobenzoyl)oxy)phenyl)nonyl)phenyl) 4,4′‐(nonane‐1,9‐diyl)dibenzoate], a liquid‐crystalline oligomer exhibiting the twist‐bend nematic phase, which has a molecular length that is of comparable dimensions to the sub‐10 nm pitch determined for CB9CB, and provide new insights into the differentiation between the nano‐ and macro‐science for self‐assembling supermolecular systems.     

Equilibrium phase diagram of polystyrene and 8CB

The experimental equilibrium phase diagram of a mixture of linear polystyrene of molecular weight M_w = 44,000 g/mol and 4‐cyano‐4′‐n‐octyl‐biphenyl (8CB) is established. The three transitions smectic A‐nematic, nematic‐isotropic, and isotropic‐isotropic are observed. The first two are observed both by optical microscopy and differential scanning calorimetry (DSC) while the isotropic‐isotropic transition could be seen only via optical microscopy. Two series of samples with the same compositions were independently prepared and yielded consistent results both by microscopy and DSC. Measurements of sample compositions with less than 50 weight % of 8CB were influenced by the vicinity of the glass transition temperature (T_g) of the polymer in the mixture. This quantity is also determined by DSC as a function of composition. A single T_g is observed, which decreases with composition of the LC. Other thermodynamic quantities such as the enthalpy variations of LC in the nematic‐isotropic transition and the fraction of LC contained in the droplets are also considered. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1841–1848, 1999     

Dielectric and elastic properties of a nematic phase induced by charge transfer interaction in a binary system containing disc-shaped molecules

Abstract

The dielectric constants and the elastic coefficients for splay (K ₁) and bend (K ₃) of the charge transfer induced nematic (N_c) phase of tridecyl pentakis(phenylethynyl)phenyl ether (1) doped with different amounts of 2,4,7-trinitrofluorenone (2) were determined by studying the electric field induced bend deformation using the capacitance method. A negative dielectric anisotropy was observed. For the bend elastic constant K ₃ values up to 22 × 10^?12 N are found which are one order of magnitude higher than the respective values of discotic nematic (N_D) phases. Values of 0·6–0·8 are obtained for the ratio K ₁/K ₃; these show a minimum for the equimolar complex.     

Multiarm star block and multiarm star mixed‐block copolymers via azide‐alkyne click reaction

The synthesis of multiarm star block (and mixed‐block) copolymers are efficiently prepared by using Cu(I) catalyzed azide‐alkyne click reaction and the arm‐first approach. α‐Silyl protected alkyne polystyrene (α‐silyl‐alkyne‐PS) was prepared by ATRP of styrene (St) and used as macroinitiator in a crosslinking reaction with divinyl benzene to successfully give multiarm star homopolymer with alkyne periphery. Linear azide end‐functionalized poly(ethylene glycol) (PEG‐N₃) and poly (tert‐butyl acrylate) (PtBA‐N₃) were simply clicked with the multiarm star polymer described earlier to form star block or mixed‐block copolymers in N,N‐dimethyl formamide at room temperature for 24 h. Obtained multiarm star block and mixed‐block copolymers were identified by using ¹H NMR, GPC, triple detection‐GPC, atomic force microscopy, and dynamic light scattering measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 99–108, 2010     

Effects of polymer network on electrically induced reflection band broadening of cholesteric liquid crystals

The reflection band of polymer stabilized cholesteric liquid crystals with negative dielectric anisotropy can be broadened by DC electric fields, which was ascribed to the pitch gradient caused by the motion of the structural chirality, that is, the polymer network. They systematically varied the mixture components, such as the photo‐initiator concentration, the monomer functionality, and the chiral dopant, to explore their influences on the reflection band broadening behavior. They learned how to control the polymer network morphology and ion density, which in turn determined the reflection bandwidth. By optimizing the mixture, they have greatly enhanced the broadening effect and achieved large bandwidth at low voltages. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 835–846     

Effect of the length of the substituents on the phase structure and transition behavior of a series of laterally attached side‐chain liquid‐crystalline polynorbornenes

A series of polynorbornenes (PNBEs) with 1,4‐bis[(3′‐fluoro‐4′‐n‐alkoxyphenyl)ethynyl]benzene mesogens (n = 1–12, where n is the number of methylene units in the substituents of the mesogens) laterally attached to polymer backbones through a one‐carbon spacer were previously synthesized by the ring‐opening metathesis polymerization of the corresponding norbornene‐based monomers. Differential scanning calorimetric results showed that the first‐order transition temperatures exhibit an odd–even alternation, especially when PNBEs have lower values of n. PNBE (n = 8), similar to the previously studied PNBEs (n = 9–12), shows a smectic C (S_C) phase at room temperature (Kim, Pugh, and Cheng, Macromolecules, 33, 8983, 2000.) According to one‐ and two‐dimensional wide‐angle X‐ray scattering experiments, PNBEs (n = 2–7) exhibit a nematic (N) phase with S_C fluctuations, whereas for PNBE (n = 1), only an N phase is observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3029–3037, 2001     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Preparation of CO2‐switchable latexes using N‐[3‐(dimethylamino)propyl]‐methacrylamide (DMAPMAm)

CO₂‐switchable polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl methacrylate) (PBMA) latexes were prepared via surfactant‐free emulsion polymerization (SFEP) under a CO₂ atmosphere, employing N‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMAm) as a CO₂‐switchable, water‐soluble, and hydrolytically stable comonomer. The conversion of the SFEP of styrene reaches >95% in less than 5 h. The resulting latexes have near monodisperse particles (PDI ≤ 0.05), as confirmed by DLS and TEM. The latexes could be destabilized by bubbling nitrogen (N₂) and heating at 65 °C for 30 min, and easily redispersed by only bubbling CO₂ for a short time without using sonication. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1059–1066     

Fabrication and optical characterization of imprinted broad‐band photonic films via multiple gradient UV photopolymerization

A structured broad‐band photonic film is fabricated by a novel method using multiple gradient UV‐induced polymerization in the presence of cholesteric liquid crystals (CLCs). Here, imprinting and broadening of the reflection band of chiral nematic mesophase cells are achieved via controlled UV polymerization. The intensity gradient of UV light is modified by the distance between UV lamp and sample cell, which affects the polymerization rate and leads to the formation of imprinted helical constructions with different pitches. In this study, a comparison of new design process with traditional UV polymerization process is carried out. After seven cycles of gradient UV polymerization, the imprinted photonic construction exhibited a broadened reflection band and Bragg reflection, even for isotropic materials. Because of this, the reflection bandwidth showed a 70% improvement. Additionally, two stacked imprinted cells with different pitches can reflect incident light with a bandwidth over the visible wavelength range of 480–680 nm. A broad‐band photonic polymer film can be imprinted using multiple gradient UV photopolymerization in the presence of CLCs. Forming a UV intensity gradient and controlling the rate of photopolymerization are key factors in broadening the reflection band. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1427–1434     

Modulation of photoswitching profiles by 10,11-dialkoxymethyl substituents in c(2)-symmetric dibenzosuberane-based helicenes

A series of C₂‐symmetric, 10,11‐disubstituted dibenzosuberane (DBS)‐based helicenes 6 a – c with a common 7‐bromo‐α‐tetralin‐based bottom fragment were synthesized. Their absolute stereochemistry was determined to be 10R,11R,P after reductive desulfurization of the corresponding (10R,11R,1′S)‐episulfides with complete stereospecificity. Photoisomerization of the diastereomerically pure (P)‐ 6 c in hexane led to virtually exclusive formation of the opposite M‐form diastereomer (P/M′, <1:>99) at 290 nm. The preferential return of (M′)‐ 6 c to (P)‐ 6 c was also achieved with high selectivity (P/M′, 90:10) at 330 nm. Molecular simulations of (P)‐ 6 c and (M′)‐ 6 c with both DBS conformations suggest that the selectivities of photoswitching are controlled by the conformation of the top DBS template as evidenced by their ¹H NMR spectra. Doping 6 c into a nematic liquid crystal (E7) led to a cholesteric mesophase with modulated pitches, reversible helical senses, and with a switch memory of ternary logic.