Synthesis and mesomorphic properties of Cu-coordinating liquid crystalline polysilsesquioxanes with heptyl side groups

In order to study the influence of the concentration of a flexible group on the liquid crystal behaviour of copper-containing complexes, series of Cu-coordinated, beta-diketone-based liquid crystalline polysilsesquioxanes (abbr. H-DK-Cu) and random copolymethylsilsesquioxanes (abbr. Me-DK-Cu), have been synthesized by the hydrosilylation reaction of a vinyl-terminated beta-diketone and 1-heptene with the polyhydrosilsesquioxane (H-T) and with the random copolymethylhydrosilsesquioxane (Me-T), followed by reaction with Cu(NH₃)₄Cl₂. Their mesomorphic properties were investigated by differential scanning calorimetry and optical polarizing microscopy. The H-DK-Cu and Me-DK-Cu complexes with M_w of approximately 1 x 10⁴ are thermotropic liquid crystalline polymers and their clearing temperature and mesophase ranges are lower than those of the corresponding Cu-coordinated, beta-diketone-based liquid crystalline polymethylsilsesquioxanes (Cu-FBDKLCP) without the n-heptyl flexible group. However, their liquidity within the temperature range of the liquid crystal state is better. The results are mainly attributed to the heptyl, flexible side group.     

Palladium complexes of side‐chain liquid crystal polymers with T‐shaped two‐dimensional mesogenic units

A series of liquid crystal polymers (LCPs) with T‐shaped two‐dimensional mesogenic units were synthesized via solution polycondensation. The LCPs were used as ligand polymers to coordinate with palladium dichloride, by which a series of polymeric palladium complexes were prepared. The liquid crystalline behaviors of the compounds were characterized using differential scanning calorimetry, polarized microscopy and X‐ray diffraction. The entire palladium complexes went to liquid crystal phase when heated to their melting temperature (T _m), and a threaded texture was observed. The melting point of all the complexes changes regularly with the increase of the end alkoxy group length and the flexible spacer unit in the ligand polymer. It is worth noting that some of the complexes without end substituent groups in the ligand polymer were also found to show liquid crystal behaviors, which would be a subject for further investigation. Copyright © 2001 John Wiley & Sons, Ltd.     

含二苯并-18-冠-6酰胺型液晶冠醚钾配合物的合成和性质

合成了2个系列酰胺型液晶冠醚钾配合物，配合物的结构通过元素分析、IR、UV-Vis和AAS等方法表征。液晶行为通过DSC、POM、XRD等方法表征。实验结果表明，所有配合物均具有热致液晶性，且随分子末端烷氧基碳原子数增加，其熔点和清亮点呈规律性变化。与配体相比，配合物液晶态温度范围变宽。液晶相态类型发生改变，配体只有近晶相，而配合物既有近晶相，又有向列相。     

SYNTHESIS AND PROPERTIES OF METAL COMPLEXES OF β-DIKETONE BASED SIDE CHAIN LIQUID CRYSTAL POLYSILOXANE

A new type of metal coordinated liquid crystalline polymers has been synthesized by complexation of metal ions with β-diketone based side chain liquid crystal polysiloxane (DKLCP). The complexation of copper ions with DKLCP greatly increases the phase transition temperature T_k from crystalline state to liquid crystalline state and T_(cl) from LC to isotropic state and makes the range of phase transition ΔT (ΔT=T_(cl)-T_k) widened. These complexes are soluble in common organic solvents. However, the incorporation of europium ions into DKLCP molecules gives rise to reduction in liquid crystallinity and crosslinking in some cases. The DKLCP coordinated with suitable amount of Eu ions can show good liquid crystallinity and fluorescent property.     

NMR研究N-甲基咪唑与双过氧钒配合物的相互作用

为探讨过氧钒配合物上有机配体对反应平衡的影响, 在模拟生理条件下(0.15 mol/L NaCl溶液), 应用多核(¹H, ¹³C和⁵¹V)多维(COSY) NMR以及变温技术等谱学方法研究双过氧钒配合物[OV(O₂)₂LL']ⁿ− [n＝1～3, LL'＝oxalate (缩写为oxa)、picolinate(缩写为pic)、bipyridine(缩写为bipy)和1,10-phenanthroline(缩写为phen), 与它们配位的含钒物种分别缩写为bpV(oxa), bpV(pic), bpV(bipy)和bpV(phen)]与N-甲基咪唑(缩写为N-Me-Im)的相互作用, 实验结果表明N-Me-Im与4种双过氧钒配合物的反应活性从强到弱的顺序为: bpV(oxa)＞bpV(pic)＞bpV(bipy)＞bpV(phen). 研究表明金属中心上配体的配位能力和空间位阻都对反应平衡产生较大的影响, 同时竞争配位的结果导致新的过氧物种[OV(O₂)₂(N-Me-Im)]⁻的生成, 而利用上述谱学方法则有助于揭示此类相互作用体系的反应过程和配位方式.     

Synthesis and mesomorphic properties and optical behaviour analysis of homologous series azobenzene liquid crystal monomer with polar substituents

ABSTRACT

Twenty novel azobenzene liquid crystal micromolecular compounds named ω-[4-(p-substituted azobenzeneoxy carbonyl]acid (X-ABCnA) have been designed and synthesised, followed by studies on the thermal performance and mesomorphic properties of the compounds. The liquid crystal compounds were divided into five homologous series based on the terminal substituents R (R = CH₃O, CH₃, H, Cl, NO₂). In each series, the number of carbons on flexible chain was 4, 6, 8 and 10, respectively. Fourier-transform infrared, proton nuclear magnetic resonance and elementary analysis demonstrated that the structure of the synthesised azobenzene liquid crystal compounds was consistent with the molecular design. The mesomorphic properties were tested, analysed and characterised by using differential scanning calorimetry and polarised optical microscopy. The melting transition (T _m) of all the compounds in homologous series with different substituents appeared to decrease with the increase of carbon numbers on flexible chains. The same held true for the temperature of isotropic-mesophase/crystalline transition. The compounds with stronger polarity of terminal substituents were more likely to form broader mesogenic ranges. The liquid crystal compounds discussed in this work can be regarded as a reference for the synthesis of mesogenic arms participating in the synthesis of novel multi-arm liquid crystalline macromolecules and polymers.     

Syntheses and mesomorphic properties of new oxygen-bridged dicopper complex homologous derived from azo-containing salicylaldimine Schiff base ligands

The synthesis, characterization and liquid crystal properties of a homologous series of new tridentate 5-((4-ⁿalkoxyphenyl) azo)-N-(3-ydroxypropyl) salicylaldimine ligands (alkoxy = octloxy, decyloxy, dodecyloxy and tetradecyloxy) and their dicopper(II) complexes are reported. These ligands were prepared by the condensation of the 5-((4-ⁿalkoxyphenyl)azo)salicylaldehydes homologous with 3-amino-1-propanol. The ligands and their dicopper complexes have been characterized by IR, ¹H NMR, mass spectroscopy and elemental analyzes. The liquid crystalline properties of the ligands and the related dicopper complexes were studied by differential scanning calorimetry (DSC) and by using a polarizing microscope equipped with a heating and cooling stage. None of the free ligands exhibit liquid crystalline behavior but all of the dicopper complexes demonstrate a smectic A mesophase.     

Influence of transitional metal ions on lyotropic liquid crystals of hydroxyethyl cellulose acetate in N,N-dimethylformamide

The influence of inorganic salts on the formation of lyotropic liquid crystals of hydroxyethyl cellulose acetate (HECA) in N,N′dimethylformamide (DMF) was studied. In the presence of CaCl₂, an inorganic salt of a principal group metal, the solution of HECA/DMF/CaCl₂ was a biphasic system. The temperature of the transformation from the liquid crystalline phase to the isotropic one increased with adding CaCl₂ because local HECA concentration increases in the HECA/DMF phase. When CuCl₂ or CoCl₂, inorganic salts of transitional metals, was added, the solutions were monophasic systems and the complexes of HECA with Cu²⁺ or Co²⁺ were formed in solutions, which results in the increase of the temperature of the transfomation from the liquid crystalline phase to the isotropic one.     

SYNTHESIS AND MESOMORPHIC PROPERTIES OF FISHBONE-LIKE LIQUID CRYSTALLINE POLYSILSESQUIOXANES——Ⅰ. FISHBONE-LIKE, β-DIKETONE-BASED LIQUID CRYSTALLINE POLYSILSESQUIOXANES AND THEIR COPPER COMPLEXES*

Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone.     

Synthesis and characterisation of star-shaped liquid crystalline polymer with a POSS core

The star-shaped POSS-graft-LCP with POSS as the core and liquid crystal polymer, poly{6-(4?-octyloxyphenyl-4″-benzoyl)hexyl acrylate}, as arms was prepared by atom transfer radical polymerisation technique using octa(3-chloropropyl) polyhedral oligomeric silsesquioxane [POSS-(CH₂CH₂CH₂Cl)₈] as initiator. For comparison, the linear liquid crystal polymer, poly{6-(4?-octyloxyphenyl-4″-benzoyl)hexyl acrylate} (LLCP), was obtained by conventional radical polymerisation. Both liquid crystal polymers were characterised by FT-IR, ¹H NMR, ¹³C NMR, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, polarised optical microscopy and X-ray diffraction analysis. The liquid crystal phase behaviour research demonstrated that both liquid crystal polymers were reversible thermotropic nematic liquid crystal materials. The number of polymerisation degree of every arm attached on POSS in POSS-graft-LCP impacted greatly on the liquid crystal properties and only a small one was necessary for it to exhibit a broad liquid crystal range. Results further demonstrated that the special star-shaped topology of POSS and the eight arms attached helped POSS-graft-LCP form and stabilise liquid crystal phase easily. This research may further expand the way to star-shaped LCPs by employing a variety of (meth)acrylate and other vinyl liquid crystalline monomers.     

Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate): synthesis and characterisation

Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate) was investigated. The novel liquid crystal was synthesised via ring-opening polymerisation of trimethylene carbonate initiated by cholesteryl derivative with an alkyl spacer and end primary hydroxyl group, without any catalyst. The chemical structure of resulting polymers was verified by ¹H NMR. Liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry, and polarising optical microscopy. The results showed that all the synthesised polymers Chol-(CH₂)₂-(TMC)_n exhibited mesomorphism in particular temperature ranges because of the introduction of the cholesteryl derivative moiety.     

Calorimetric study of the isotropic to nematic phase transition in an aligned liquid crystal nano‐colloidal gel

A high‐resolution calorimetric study of the specific heat (C_p ) has been carried out for the isotropic to nematic phase transition in an aligned liquid crystal (octylcyanobiphenyl ‐ 8CB) and aerosil nano‐colloid gel. A stable alignment was achieved by repeated thermal cycling of the samples in the presence of a strong uniform magnetic field, which introduces anisotropy to the quenched random disorder of the silica gel. In general, the specific heat features of the I?N transition in aligned (anisotropic) gel samples are consistent with those seen in random (isotropic) gel samples, namely the observance of two C_p peaks and non‐monotonic transition temperature shifts with increasing silica concentration. However, larger transition temperature shifts with silica density, modification of the phase conversion process in the two‐phase coexistence region, and a larger effective transition enthalpy are observed for the aligned samples. The lower‐temperature aligned C_p peak is larger and broader while exhibiting less dispersion than the equivalent peak for the random gel. This may be a consequence of the alignment altering the evolution from random‐dilution‐dominated to random‐field‐dominated effects. The exact origin of the larger transition temperature shifts is uncertain but the larger enthalpy suggests that the nematic state is different in the aligned system than in random gels. The general non‐monotonic behaviour of the transition temperature is interpreted using dimensional analysis as a combination of an effective elastic stiffening of the liquid crystal combined with a liquid crystal and aerosil surface interaction energy.     

A new type of liquid crystal involving hydrogen bonding: single crystal X-ray structure characterization and properties of the liquid crystal

A new liquid crystal involving hydrogen bonding between 4-hexyloxybenzoic acid and 4-octyloxylphenylethynylpyridine has been investigated by DSC, polarizing optical microscopy and X-ray diffraction. The mesogen shows a nematic phase and an unknown liquid crystalline phase. The liquid crystal crystallizes with a triclinic space group P-1 with the parameters: a = 8.879(2)Å, b = 10.137(2)Å, c = 17.629(4)Å; α = 104.16(3)°, β = 95.47(3)°, γ = 101.48(3)°; V = 1490.3(6)ų; Z = 2; F(000) = 572; μ = 0.076 mm^?1; λ(MoK_α) = 0.71073 Å; final R ₁ = 0.0435. The complex is formed by strong intermolecular hydrogen bonding.     

Invited Lecture. Ferroelectric liquid crystalline polymers and related model compounds with a low–moderate degree of polymerization

Abstract

Ferroelectric liquid crystalline polymers (FLCPs) with a low-moderate degree of polymerization were synthesized. These had a comb structure; the main chain was polyacrylate and the side chain consisted of a flexible spacer, a core and an optically active chiral end group. They exhibited electro-optic switching times ranging from a few milliseconds to a few seconds in the S*_c phase. As the molecular weight M _n increased, the range of the S*_c shifted to higher temperatures. At a given temperature, the switching time increased with M _n .

Spontaneous polarizations P _s , apparent cone angles 2θ, electro-optic switching times τ and rotational viscosities η of some polyoxyethylene FLCPs and corresponding low molecular weight ferroelectric liquid crystal materials (FLCs) were also measured. This is the first report of polyoxyethylene FLCPs. There was no significant difference in P _s and 2θ, which shows that the arrangement of the side chains in the FLCP is similar to that of the molecules in ordinary FLC. On the contrary, τ and η for the FLCPs were 10²–10³ times as large as those for FLCs. The rotational viscosity of the FLCP was mainly dependent on the side chain structure rather than on the spacer. Therefore collisions between adjacent side chains cause large η values in FLCPs rather than hindrance to side chain gyration due to the spacer group. By combining FLCPs with ITO-coated plastic substrates, a large area matrix driven display has been made. Although an improvement in switching time is still needed, a flexible and lightweight display like a sheet of paper will be available in the near future.     

Heterocyclic Bismuth(III) Dithiocarbamato Complexes as Single‐Source Precursors for the Synthesis of Anisotropic Bi2S3 Nanoparticles

New complexes catena‐(μ₂‐nitrato‐O,O′)bis(piperidinedithiocarbamato)bismuth(III) ( 1 ) and tetrakis(μ‐nitrato)tetrakis[bis(tetrahydroquinolinedithiocarbamato)bismuth(III)] ( 2 ) were synthesised and characterised by elemental analysis, FTIR spectroscopy and thermogravimetric analysis. The single‐crystal X‐ray structures of 1 and 2 were determined. The coordination numbers of the Bi^III ion are 8 for 1 and ≥6 for 2 when the experimental electron density for the nominal 6s² lone pair of electrons is included. Both complexes were used as single‐source precursors for the synthesis of dodecylamine‐, hexadecylamine‐, oleylamine and tri‐n‐octylphosphine oxide‐capped Bi₂S₃ nanoparticles at different temperatures. UV/Vis spectra showed a blueshift in the absorbance band edge characteristic of a quantum size effect. High‐quality, crystalline, long and short Bi₂S₃ nanorods were obtained depending on the thermolysis temperature, which was varied from 190 to 270 °C. A general trend of increasing particle breadth with increasing reaction temperature and increasing length of the carbon chain of the amine (capping agent) was observed. Powder XRD patterns revealed the orthorhombic crystal structure of Bi₂S₃.     

Thermal and Emission Properties of a Series of Lanthanides Complexes with N-Biphenyl-Alkylated-4-Pyridone Ligands: Crystal Structure of a Terbium Complex with N-Benzyl-4-Pyridone

This work focuses on the investigation of the liquid crystalline behavior and luminescence properties of the lanthanide complexes of Eu(III), Sm(III) and Tb(III) with N-biphenyl-alkylated-4-pyridone ligands. The organic ligands having a biphenyl group attached via a long flexible spacer with either 9 or 10 carbon atoms were synthesized by the reaction between 4-hydroxypyridine and the corresponding bromide compounds. The chemical structures of the organic and lanthanide complexes were assigned based on elemental analysis, single-crystal X-ray diffraction, ¹H, ¹³C NMR and IR spectroscopies, and thermogravimetric analysis (TGA). The X-ray diffraction analysis of a parent compound shows that the lanthanide ions are surrounded by three monodentate pyridone ligands and three bidentate nitrate ions, giving a 9-coordinate environment. The mesogenic behavior and the type of liquid crystalline phases exhibited by the new complexes were analyzed by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM), and powder X-ray diffraction (XRD) studies. Only the lanthanide complexes with longer spacer (10) display a monotropic SmA phase, typically on a short thermal range (less than 10 °C). The complexes with shorter flexible chains (9) show no liquid crystalline properties with melting temperatures lower than their analogs with longer spacers. The emission spectra recorded in solid state at room temperatures show typical emission bands for each lanthanide ion employed (Eu(III), Tb(III) and Sm(III)).     

Liquid Crystalline Behaviours of the Complexes Based on 1,3,4‐Oxadiazole Derivative and Benzoic Acid

A non‐liquid crystal compound (4‐POXD‐6) containing the 1,3,4‐oxadiazole group and pyridyl (py) group was synthesized. And a series of supramolecular mesogenic complexes were obtained by mixing 4‐POXD‐6 and 4‐alkoxybenzoic acids (Cn, n=6, 8, 12). The liquid crystalline properties of 4‐POXD‐6/Cn (n=6, 8, 12) were investigated by means of differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray diffraction. It was found that 4‐POXD‐6/Cn (6, 8) display monotropic nematic and smectic A phases, while 4‐POXD‐6/C12 exhibits a SmX phase in the heating process and a SmA phase in the cooling run. Variable‐temperature FTIR spectroscopic studies revealed hydrogen bonds existed in both crystalline and liquid crystalline phases.     

Synthesis of polystyrene-polysiloxane side-chain liquid crystalline block copolymers

The synthesis of a new liquid crystalline block copolymer consisting of a polystyrene block and a side-chain liquid crystalline siloxane block is reported. The synthetic approach described is based on the anionic polymerization of styrene and cyclic trimethyltrivinyltrisiloxane monomers, followed by functionalization of the siloxane block with side chain mesogens. The siloxane block has a T_g well below 25°C and is designed to exhibit a chiral smectic C^* phase at room temperature. These block copolymers are the first side-chain liquid crystalline block copolymers which contain both a high T_g glassy block and a low T_g liquid crystalline block.     

Luminescent fluorinated chiral liquid crystalline oligomers containing Eu(III) complexes

Luminescent ?uorinated chiral liquid crystalline oligomers containing Eu(III) complexes (Eu-LCOs) with good liquid crystalline properties and obvious luminescence properties were prepared using Poly(methylhydrogeno)siloxane (PMHS), chiral liquid crystalline monomer (M₁), ?uorinated liquid crystalline monomer (M₂), ?uorinated Eu(III) complex (M₃). The chemical structures, liquid crystalline behaviours of Eu-LCOs were characterised by various experimental techniques. The introduction of small quantity of ?uorinated Eu(III) complexes endowed the oligomers with excellent luminescence properties. The Eu(III) complexes did not change the liquid crystalline textures of the oligomers. Fourier transform infrared imaging showed that Eu(III) complexes were evenly distributed in oligomers. In order to express the mutual effect and distribution of the components, a structural representation of Eu-LCOs was established. The Eu-LCOs displayed wide mesophase temperature ranges and reversible mesomorphic phase transitions. The Eu-LCOs can emit soft red light when being excited. Luminescence intensities of Eu-LCOs gradually increased with an increase of Eu(III) complexes from 0 to 1.0 mol%. However, the luminescence intensities of Eu-LCOs decreased monotonically with the increase of temperature in liquid crystalline phase.     

Synthesis and characterisation of polymethacrylates containing para-, meta- and ortho-monosubstituted azobenzene moieties in the side chain

Three sets of novel side-chain liquid crystalline polymers with monosubstituted azobenzene moieties in the side-chain have been studied. These are poly(p-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PPHABM), poly(m-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (PMHABM) and poly(o-(4′-methoxy-4-oxyhexyloxy azobenzene) benzyl methacrylate) (POHABM). The chemical structure of the monomers was confirmed by ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The structural characterisation of the polymers was performed by ¹H NMR spectroscopy and gel permeation chromatography, and their phase behaviour and liquid crystalline properties were studied using differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. The results show that the transitional behaviour of side-chain liquid crystalline polymers containing monosubstituted azobenzene moieties depends strongly on the position of the substituent on the azobenzene moiety; for example, the ortho-monosubstituted polymers do not form liquid crystalline phases, but all the para- and meta-monosubstituted polymers exhibit a smectic A phase. Furthermore, the glass transition temperature (T_g ) of the polymers decreases in the order, para > meta > ortho. For the PPHABM and PMHABM polymers the isotropic temperature (T_i ) and liquid crystalline range (ΔT, from T_g to T_i ) are found to be in the order, para > meta, although it is surprising that the associated enthalpy changes in these polymers is the opposite order, meta > para.