Mesomorphic amino sugars

New liquid crystalline compounds have been prepared from glucosamine and 6-amino-6-deoxy-hexopyranoses. The monoalkylated carbohydrates show smectic phases. The influence of the amino group on the clearing temperatures is minor. The salts of the cyclic amines can form smectic or discotic mesophases. The clearing points are lower than those observed for acyclic amines.     

Mesomorphic Complex Compounds

This paper presents a review of liquid crystalline complexes whose central atoms are d elements (Group IB, IIB, IIIB, or VB atoms), f elements (lanthanides), and s or p elements. The possibilities of constructing coordination compounds with mesomorphic properties are discussed in view of the central atom coordination number and the nature of the ligand.     

Mesomorphic N-alkylpyridinium dodecylsulphates

Reaction of pyridine with 1-bromoalkanes leads to N-alkylpyridinium bromides which can be further reacted with silver dodecylsulphate to give N-alkylpyridinium dodecylsulphates in good yield. These salts are mesomorphic and their mesophases have been characterized by optical microscopy, DSC and X-ray scattering techniques.     

Mesomorphic ordering of polymers

Depending upon their chemical architecture, polymers may give rise to well - ordered mesomorphic phases. A few typical examples of mesomorphic polymers (block copolymers, polysoaps and side-chain liquid - crystalline polymers, rigid-chain polymers) will be considered. Their structure will be described as determined by x-ray diffraction.     

Mesomorphic Crown Ethers

Studies on mesomorphic crown ethers, their analogs, published during the past two decades'are briefly summarized and correlated. Speicific features of mesophase formation, as influenced by the structure of the macrorings, are analyzed. The effect of structural factors on formation of various types of liquid crystals is discussed. Published data on prediction of formation of columnar mesophases in cyclic polyethers using quantitative molecular parameters are analyzed. Synthetic routes to such compounds are briefly presented. Particular attention is given to structure, properties, and possible applications of mesomorphic macrocycles.     

Mesomorphic behaviour of 1,3-phenylene bis[4-(4-alkoxyphenyliminomethyl)benzoates] and related compounds

DSC and X-ray diffraction studies on a series of 1,3-phenylene bis[4-(4-alkoxyphenyliminomethyl)benzoates] are presented. The only mesophase exhibited by the methoxy to hexadecyloxy homologues is of the smectic C type. The reversal of the iminomethyl linkage reduces drastically the incidence of a mesophase; that is, only the first five homologous members exhibit a smectic C phase in the series of 1,3-phenylene bis[4-(4-alkoxybenzylideneamino)benzoates]. Almost all the members in the second series become nematogenic by the chloro substitution at the 4-position of the 1,3-phenylene moiety. In addition, a smectic C phase is observable for the ethoxy to pentyloxy and also the tetradecyloxy and hexadecyloxy members. The second chloro-substituent introduced to the 6-position of the same central ring eliminates completely the smectic C phase and enhances the nematic thermal stability.     

Confinement effects on the self-assembly of 1,3:2,4-Di-p-methylbenzylidene sorbitol based organogel

1,3:2,4-di- p-methylbenzylidene sorbitol (MDBS) is a small organic molecule that is capable of inducing self-assembly in a wide variety of organic solvents and of forming organogels. In this paper, we present a novel approach to tune the network architectures of organogels by utilizing geometric confinement while varying the gelator concentration. Self-assembly of MDBS in propylene carbonate (PC) is investigated in a series of microchannels with widths varying from 20 to 80 mum and the gelator concentration varying from 2 to 7 wt %. We demonstrate by optical microscopy and scanning electron microscopy (SEM) that a transition from fibrillar structure to sheaflike spherulite structure occurs when (a) the channel width is increased for fixed gelator concentrations and (b) gelator concentration is increased for fixed channel widths. A phase diagram is built based on these observations. Polarized microscopy and transmission electron microscopy (TEM) images are also obtained for organogel under unconfined condition to display the spherulite structures viewed under different length scales. The thermal properties of the organogel are measured by differential scanning calorimetry (DSC) to verify the structural difference obtained under confined and unconfined conditions and the structure stability. Our results provide a novel strategy to control the topological structure of self-assembled systems and to modify their thermal properties via geometric confinement.     

具有液晶相态特征的功能化梯形聚硅氧烷

介绍了几种具有液晶相态特征的功能化梯形聚硅氧烷，包括β－二酮、西夫碱、偶氮３种类型液晶侧链的“鱼骨形”液晶高分子和相应的金属络合型液晶高分子以及挂接发色团的非线性光学梯形高分子。它们是由反应性聚氢基倍半硅氧烷及其共聚物与功能性单体进行硅氢加成反应来合成的。“鱼骨形”液晶高分子与小分子液晶组成高分子网络液晶（ＰＮＬＣ）型的复合物，表现出有趣的正性或负性两种不同的电光响应行为，与“锚泊效应”和弹性有关。非线性光学梯形高分子的极化膜表现了稳定的极化诱导取向。高温下稳定的双折射光带为这类梯形高分子共同的相态特征之一。可控孔径尺寸的笼状自组装超分子膜及其与有机小分子构成的分子级功能复合膜为逐步偶联聚合方法的另一重要发展方向。     

Mesomorphic properties of some 1,4,8,11,15,18,22,25-octa-alkoxymethylphthalocyanines

Abstract

The mesophase behaviour of a number of non-peripherally octa-substituted phthalocyanine derivatives has been studied by optical microscopy, differential scanning calorimetry (DSC) and X-ray diffraction. A homologous series of straight chain alkoxymethyl derivatives has exhibited both rectangular and hexagonal columnar mesophases, with the rectangular phases being favoured by the shorter chains. Two branched chain derivatives were found to give rectangular columnar phases at room temperature. A detailed analysis of the X-ray data has shown some differences from the analogous n-alkyl compounds. It has been deduced that the increased polarizability and flexibility of the ether linkage allows the disc-like molecules to approach more closely face to face with correspondingly thicker columns.     

Spontaneous reaction and self-assembly of copper nitrate and cyclic 1,3-dione dioximes into multicopper complexes

We have found that Cu(NO₃)₂ and 1,3-dione dioxime afford a variety of multicopper complexes under ambient conditions. Specifically, Cu(NO₃)₂ and cyclohexane-1,3-dione dioxime gave a trinuclear complex in which the central α-carbons of the three dioxime ligands are oxidized into carbonyl groups, two of which were further reacted with solvent MeOH to give a hemiacetal structure. On the other hand, Cu(NO₃)₂ and cyclopentane-1,3-dione dioxime gave a dinuclear complex in which Cu(II) was reduced to Cu(I) and two of the three ligands couple to give the fulvalene structure. Together with the previously reported reaction of Cu(NO₃)₂ and pentane-2,4-dione dioxime into a pentanuclear complex in which the four ligands were changed into trioximes, surprisingly rich chemistry has been discovered for combinations of Cu(NO₃)₂ and 1,3-dione dioximes.     

Mesomorphic properties of achiral halogen-substituted banana-shaped compounds

Three banana-shaped achiral compounds, derivatives of 4,6-dichloro-1,3-phenylene bis-[4-(4- n -octyloxyphenyliminomethyl) benzoate], were synthesized by varying the substituent ( X =H, F and Cl). Their mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray analysis. The compound with X = H exhibited an enantiomeric nematic phase. The compounds with X = F and Cl formed a nematic phase on heating, while on cooling they formed a nematic phase at high temperature and a smectic A phase at a lower temperature (monotropic). A schematic representation of the mesophase structures for the compound with X = F is also illustrated.     

Mesomorphic structures of protonated surfactant-encapsulated polyoxometalate complexes

Keggin-type heteropolyanions, H(3)PW(12)O(40) (HPW), Na(3)PW(12)O(40) (NaPW), H(4)SiW(12)O(40) (HSiW) and K(4)SiW(12)O(40) (KSiW), were encapsulated by a cationic surfactant, di[12-(4'-octyloxy-4-azophenyl)dodecyloxy]dimethylam monium bromide (L), through the replacement of counterions. The resulting surfactant-encapsulated polyoxometalate complexes were characterized by UV-vis, Raman, and NMR spectra in detail. The measurement results indicated that some azobenzene groups of the surfactant were protonated in the complexes HL/HPW (HL is the abbreviation of the protonated surfactant), HL/NaPW, and HL/HSiW during the process of encapsulation, whereas the protonation was not observed in L/KSiW. The thermotropic liquid crystal properties of these complexes were investigated by differential scanning calorimetry, polarized optical microscopy and variable-temperature X-ray diffraction. Interestingly, different smectic mesophases were observed between the protonated HL/HSiW and the non-protonated L/KSiW, which suggests that the protonation of azobenzene groups in HL/HSiW plays a key role in the liquid crystalline organization. However, protonated HL/HPW and HL/NaPW exhibit a similar smectic B phase to that of the de-protonated one, L/HPW. A competitive balance between the phase separation and the volume minimization of surfactants was proposed to explain the self-organized liquid crystal structures of these protonated and non-protonated complexes. To the best of our knowledge, the present investigation provides a specific example for protonated hybrid materials with stable liquid crystal properties.     

Mesomorphic properties of side-chain cholesteric liquid-crystalline elastomers

New monomer cholesteryl 4-(10-undecylen-1-yloxybenzoyloxy)-4′-ethoxybenzoate (M₁), crosslinking agent biphenyl 4,4′-bis(10-undecylen-1-yloxybenzoyloxy-p-ethoxybenzoate) (M₂) and a series of side-chain cholesteric elastomers were prepared. The chemical structures of the monomers and elastomers obtained were confirmed by element analyses, FT-IR, and ¹H NMR. The mesomorphic properties and thermal stability were investigated by 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. M ₁ showed cholesteric phase, and M ₂ displayed nematic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Mesomorphic properties of achiral halogen-substituted banana-shaped compounds

Three banana-shaped achiral compounds, derivatives of 4,6-dichloro-1,3-phenylene bis-[4-(4-n-octyloxyphenyliminomethyl) benzoate], were synthesized by varying the substituent (X = H, F and Cl). Their mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray analysis. The compound with X = H exhibited an enantiomeric nematic phase. The compounds with X = F and Cl formed a nematic phase on heating, while on cooling they formed a nematic phase at high temperature and a smectic A phase at a lower temperature (monotropic). A schematic representation of the mesophase structures for the compound with X = F is also illustrated.     

手性主链液晶离聚物的液晶性能

以6,6'-二羟基麦芽糖六乙酸酯(MA)、4,4'-对羟基联苯酚(MB)、2,5-二羟基苯甲酸(MC)、癸二酰氯(SD)为单体,采用溶液缩聚的方法合成了主链液晶离聚物.通过红外光谱、差示扫描量热及偏光显微等手段,研究了MC含量对液晶离聚物性能的影响.结果表明:液晶聚合物均为热致胆甾型,随MC含量的增加,其玻璃化转变温度、熔点和清亮点呈上升趋势,液晶相逐渐被破坏,羧酸离子的引入没有改变聚合物的液晶相类型.     

Mesomorphic flexible chain polymers based on silicon

Poly(dialkylsiloxane)s and poly(dialkylsilane)s form a similar type of columnar mesophase. Although, the polysilanes are stiffer than polysiloxanes, both classes of polymers may be considered to be flexible due to the ability to form chain-folded crystals. Chain flexibility rather than the presence of chain stiffness determines whether the columnar mesophase is formed. A certain amphiphilic character does not appear to be required, as polysiloxanes with short side groups, e.g. polydiethylsiloxane display the same mesophase behaviour as polydialkylsilanes with long side chains and other nonpolar flexible chain molecules. The importance of the entropy gain upon conformational disordering is reflected in the increase in temperature stability with increasing alkyl side group length and the absence of mesophase behaviour in the case of the dimethyl substituted polymers     

Synthesis and Mesomorphic Properties of 2,6-Disubstituted Tetralins

Synthesis and mesomorphic behavior of nine members of each of the two classes of 6-phenyl- and 2-phenyltetralins and five members of the 2-trans-cyclohexyltetralins are reported. The synthesis of one member of each class is described in detail. Besides the target compounds, more than twenty intermediates showed liquid crystalline properties; their transition temperatures are recorded (see Tables 1-6).     

Mesomorphic behaviour of praseodymium(III) alkanoates

In this paper, we describe the synthesis, characterization and thermal behaviour of praseodymium(III) alkanoates. The compounds have the stoichiometry [Pr(C_xH_2x+1COO)₃], where x = 5-19, and were characterized by elemental analysis and infrared spectroscopy. The thermal behaviour was investigated by hot-stage polarizing optical microscopy, DSC and high temperature X-ray diffraction. A highly viscous mesophase M and a smectic A phase were observed for the shorter chain compounds (x = 5-8), whereas only a smectic A phase was observed for the longer chain compounds of this type of metallomesogens. The chain length has a pronounced effect on the transition temperatures.     

Mesomorphic behaviour of praseodymium(III) alkanoates

In this paper, we describe the synthesis, characterization and thermal behaviour of praseodymium(III) alkanoates. The compounds have the stoichiometry [Pr(C _x H_2x+1COO)₃], where x = 5-19, and were characterized by elemental analysis and infrared spectroscopy. The thermal behaviour was investigated by hot-stage polarizing optical microscopy, DSC and high temperature X-ray diffraction. A highly viscous mesophase M and a smectic A phase were observed for the shorter chain compounds (x = 5-8), whereas only a smectic A phase was observed for the longer chain compounds of this type of metallomesogens. The chain length has a pronounced effect on the transition temperatures.