新型笼状钼磷超分子化合物的水热合成与晶体结构

用水热法首次合成了含有２ 种有机胺的新型笼状钼磷超分子化合物〔ＮＨ３（ＣＨ２）６ＮＨ３〕７〔ＮＨ３（ＣＨ２）２ＮＨ３〕２（Ｈ３Ｏ）６〔Ｐ２ Ｍｏ５Ｏ２３〕４·１１Ｈ２Ｏ,并通过元素分析、红外和Ｘ－ 射线单晶衍射法进行了结构表征．晶体属三斜晶系,空间群ｐ１杂多阴离子中的每个〔Ｐ２Ｍｏ５Ｏ２３〕６－ 是由５ 个ＭｏＯ６ 八面体和两个ＰＯ４ 四面体键合而成,其中Ｍｏ,Ｐ原子成一个畸变五角双锥构型．     

Polymorphism and structure in different kinds of liquid crystal polymers and copolymers

We report a short outline of chain-conformation informations obtained by small angle neutron scattering (SANS) studies of different kinds of Liquid Crystalline Polymers (LCPs). We conclude that in the nematic phase the prolate shape of the chains are directly connected to the orientational order and the magnitude of the chain extension strongly depends on molecular parameters relative to the coupling mesogen-chain. The behavior is markedly different when the backbone anisotropy is oblate shape due to the chain confinement between the smectic layers.     

Synthesis, crystal structure and thermal decomposition of a novel praseodymium supermolecular complex

A novel complex, [Pr(5-nip)(phen)(NO3)(DMF)] (5-nip: 5-nitroisophthalic acid; phen: 1,10-phenanthroline, DMF: N,N-dimethylformamide), was prepared and characterized by single crystal X-ray diffraction, elemental analysis, IR spectrum and DTG-DSC techniques. The results show that the crystal is monoclinic, space group P2(1)/n with a=11.0876(6) Å, b=12.8739(7) Å, c=16.9994(8) Å; β=91.193(4)°, Z=4, D _c=1.822 Mg m^–3, F(000)=1320. Each Pr(III) ion is nine-coordinated by one chelating bidentate and two monodentate bridging carboxylate groups, one chelating bidentate nitryl group, one DMF molecule and one 1,10-phenanthroline molecule. The complex is constructed with one-dimensional ribbons featuring dinuclear units and the one-dimensional ribbons are further assembled into two-dimensional networks by strong π–π stacking interactions. The complex has high stability up to 500°C. The enthalpy change of formation of the compound in DMF was measured using an RD496-III type microcalorimeter with the value of –9.214±0.173 kJ mol^–1.     

Studies of the structure of blends containing two liquid crystal polymers

Blends in which both of the component materials are capable of forming liquid crystalline phases are considered in the present work. Solid-state characterization data are presented that suggest that chemical reaction is not a dominant event when two such materials are blended in the melt. Also, ideas of small-molecule liquid crystal mixing are shown to be not applicable to describe the behavior of this system. A formalism for describing blends of liquid crystal polymers, based on Windle's sequence matching arguments, is proposed.     

On the structure and the chain conformation of side-chain liquid crystal polymers

Abstract

Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R _⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate backbone conformation in the smectic phase is always larger than in the nematic phase. This is attributed to a periodic distribution of the backbone between the mesophase layers. Then, the backbone anisotropy depends not only on the smectic structure (S_A1, S_Ad), but also on the temperature dependence of the density of aligned mesogenic groups in the layers. On the other hand, it is shown that the isotopic mixtures are no longer ideal when polymers deuteriated in the mesogenic moieties are mixed with the corresponding hydrogenous polymers.     

Structure and aggregation number of a lyotropic liquid crystal: a fluorescence quenching and molecular dynamics study

The structure and aggregation number of a discotic lyotropic liquid crystal, prepared from tetradecyltrimethylammonium chloride (TDTMACl)/decanol (DeOH)/NaCl/H2O, have been examined using fluorescence quenching of pyrene by hexadecylpyridinium chloride and molecular dynamics (MD). The fluorescence method gives an aggregation number of 258 +/- 25 units (DeOH + TDTMACl). From the MD simulation, a lower limit for the aggregate dimension of 130 units of DeOH + TDTMACl is predicted. A stable oblate aggregate of 240 units was studied in detail. A strong polarization between the ammonium headgroups and chloride ions is observed from the calculated trajectory. DeOH headgroups are located, on average, 0.3 nm more to the interior of the aggregate than the TDTMACl headgroup and contribute to widening the interface by forming H-bonds with water. The radial distribution function of the ammonium headgroup shows that there are 16 water molecules in the first solvation sphere. The diagonal elements of the order parameter tensor of the tail atoms of both surfactants indicate that the interior of the micelle preserves about the same degree of order as at the interface, up to the last three atoms of the aliphatic chain, where the order starts to decrease.     

Investigation of side chain liquid crystal polymers bearing cholesterol and bile acid derivatives

Cholic acid (or 3a,7a,12a-trihydoxyl-5a-cholan-24-oic acid) and lithocholic acid (or 3a-hydroxyl-5a-cholanic-24-oic acid) are commonly occurring bile acids synthesized from cholesterol in the liver in mammals. They all possess a steroid skeleton containing four rings, three with six carbons and one with five carbons. The transformation of cholesterol to cholic acid results in two major structural changes that affect the steroid skeleton. The first is the hydrogenation of the double bond between C5 and C6 and the second is a conformational flip of ring A from the 5a-position to the 5a-position. In addition, one or more hydroxyl groups are added to the steroid skeleton. Outside of the ring system, C24 is converted from a saturated alkyl to a carboxylic acid group.Side chain polymers based on cholesterol moiety have been made as reported in the literature.Since bile acids and cholesterol are all in the family of steroid molecules, it is of interest to investigate whether bile acids may also act as mesogenic groups.Therefore, flexible spacer groups with 10 carbons are introduced between bile acid skeleton and the poymerizable double bonds. The monomers and polymers are compared with cholesterol and dihydrocholesterol monomers and polymers with the same spacers. Dihydrocholesterol is chosen to investigate the influence of the double bond in the formation of LC, given that both cholesterol and dihydrocholesterol have a planar structure but there is no double bond in the latter. These monomers and their corresponding polymers were characterized for their liquid crystalline (LC) properties by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction.It was found that only the compounds bearing the planar cholesterol moieties possess LC phases. It is concluded that the 5a-configuration between the first and second cycles on the steroid skeleton of bile acids does not favor proper alignment of the rigid part of the bile acid moieties. It is interesting to see the effect of a small variation in structure on the properties of the otherwise structurally-similar compounds and the materials made from them.     

An etching technique to reveal the supermolecular structure of crystalline polymers

Highly polished surfaces of nylon 6, nylon 66, polychlorotrifluoroethylene and polypropylene were etched by aromatic and chlorinated hydrocarbons at temperatures between 25 and 75°C to reveal surface morphology. Comparison with micrographs obtained with microtomed sections shows the absence of etching artifacts which are known to accompany the use of oxidizing etching agents.     

Investigation of structure and dynamics in a photochromic molecular crystal by NMR crystallography

A photochromic anil, N-(3,5-di-t-butylsalicylidene)-4-amino-pyridine, has been studied by single-crystal X-ray diffraction, multinuclear magic-angle spinning NMR, and first-principles density functional theory (DFT) calculations. Interpretation of the solid-state NMR data on the basis of calculated chemical shifts confirms the structure is primarily composed of molecules in the ground-state enol tautomer, whereas thermally activated cis-keto and photoisomerised trans-keto states exist as low-level defects with populations that are too low to detect experimentally. Variable temperature ¹³C NMR data reveal evidence for solid-state dynamics, which is found to be associated with fast rotational motion of t-butyl groups and 180° flips of the pyridine ring, contrasting the time-averaged structure obtained by X-ray diffraction. Comparison of calculated chemical shifts for the full crystal structure and an isolated molecule also reveals evidence for an intermolecular hydrogen bond involving the pyridine ring and an adjacent imine carbon, which facilitates the flipping motion. The DFT calculations also reveal that the molecular conformation in the crystal structure is very close to the energetic minimum for an isolated molecule, indicating that the ring dynamics arise as a result of considerable steric freedom of the pyridine ring and which also allows the molecule to adopt a favourable conformation for photochromism.     

Photo-induced bending behaviour of side-on linear liquid crystal polymers with high molecular weight

ABSTRACT

Two photoresponsive side-on linear liquid crystal polymers (SLLCPs) with different spacer lengths have been synthesised through facile ring-opening metathesis polymerisation (ROMP). For the first time, high molecular weight SLLCPs with polynorbornene backbone and azobenzene side chains are obtained and processed into films by the melt shear-induced orientation method. These SLLCP films exhibit fast and large photo-induced bending behaviour, showing bend degree up to 72° in 3 s upon UV irradiation at ambient temperature. The shape of these films remains unchanged under visible light, demonstrating good shape stability against sunlight. Moreover, owing to their linear structure, the SLLCP films are recyclable through traditional melting or solution methods. Possessing these features, these SLLCP films show application prospects in the fields of light-controllable flexible actuators.     

Crosslinked liquid crystal polymers from liquid crystal monomers: Synthesis and mechanical properties

Difunctional acrylates and methacrylate monomers have been made which are high order smectic liquid crystal (or crystalline) at room temperature. This report discusses materials with the following structure: F–S–M–S–F, where F is a functional group, acrylate or methacrylate (A or M); S is a spacer (CH₂)_n(n), and M is a mesogen—in this case 4,4′-dioxybiphenyl (B). They are codified as BnA or BnM where n is the number of methylenes in the spacer. High conversion with high T_g can be obtained when polymerizing in the smectic state because the reactive end groups are concentrated in a small volume and can react well with little or no diffusion. B2A, B3A, B6A, B11A, and B3M were polymerized in the smectic state and compared to polymers made at temperatures where the monomers were isotropic. High conversion was obtained below final T_g—even then, probably because the polymers were ordered. All the polymers were studied by WAXD and dynamic mechanical spectroscopy. Solid-state NMR on B3A showed that there was very high conversion of the double bonds at all temperatures. B3A photopolymerized in the smectic state (60–76°C) produced a crystalline polymer with T_g = 185°C (1 Hz). When photopolymerized at 85°C, above the isotropization temperature (T_i), a poorly organized polymer was obtained with a T_g of 155°C (1 Hz). Monomers with an odd number of methylene groups as spacers were crystalline after polymerization. With an even number of methylene groups, they lost most of their crystallinity on polymerization below T_i, but retained a low order smectic structure. Similar structures were obtained with all the monomers when they were polymerized above T_i. There was little effect of polymerization temperature on T_g when the spacers had an even number of methylene groups. © 1993 John Wiley & Sons, Inc.     

Polymer blends containing liquid crystal polymers

Polymer blends can be either composed of mixtures of flexible components, of a stiff chain and a flexible macromolecule, or of two stiff-chain polymers. All three cases may be dealt with in terms of the Flory lattice model. Special attention is paid to the influence of liquid crystalline order on the miscibility of the two polymers. For isotropic mixtures all three cases may be described in terms of the usual Flory–Huggins approximation. If a nematic phase is formed the miscibility of blends of rigid rods with flexible macromolecules (molecular composites) is strongly reduced because of entropic reasons. Highly ordered mixture of two stiff-chain polymers in melt can be described in terms of the regular solution theory leading to the same miscibility criterion as is valid for two flexible polymers. All deductions are compared to recent experimental work.     

Photoaddressable polymers for liquid crystal alignment

We demonstrate reversible photoinduced in situ reorientation of low molecular mass liquid crystals (LCs) by means of photoaddressable polymers (PAPs). These polymers contain mesogenic azobenzene side chains optimized to reorient cooperatively and effectively upon illumination with polarized light. Various low molecular mass LCs were introduced between two PAP layers and these sandwich devices were tested with respect to stability and reversibility of photoinduced orientation. Dissolution of the PAP layer by the low molecular mass LC was observed for several material combinations and systematically investigated. Different anisotropic dyes were added as fluorescence markers in order to monitor the photoinduced LC orientation. With an optimized material combination, more than 10 reversible reorientation processes could be realized with polarized light of either 514 or 405 nm wavelength, without any reduction in alignment quality. Further, microscopic polarized fluorescence patterns could be produced and erased within short exposure times.     

Photoaddressable polymers for liquid crystal alignment

We demonstrate reversible photoinduced in situ reorientation of low molecular mass liquid crystals (LCs) by means of photoaddressable polymers (PAPs). These polymers contain mesogenic azobenzene side chains optimized to reorient cooperatively and effectively upon illumination with polarized light. Various low molecular mass LCs were introduced between two PAP layers and these sandwich devices were tested with respect to stability and reversibility of photoinduced orientation. Dissolution of the PAP layer by the low molecular mass LC was observed for several material combinations and systematically investigated. Different anisotropic dyes were added as fluorescence markers in order to monitor the photoinduced LC orientation. With an optimized material combination, more than 10 reversible reorientation processes could be realized with polarized light of either 514 or 405 nm wavelength, without any reduction in alignment quality. Further, microscopic polarized fluorescence patterns could be produced and erased within short exposure times.     

Influence of molecular weight on liquid crystalline behavior of linear and star mesogen‐jacketed liquid crystal polymers

A series of novel multi‐armed (di‐, tri‐ and tetra‐armed) mesogen‐jacketed liquid crystal polymers (MJLCPs) were synthesized by atom transfer radical polymerization (ATRP) of {2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}(MPCS) using di‐, tri‐ and tetrafunctional initiator, respectively. The results show that the number average molecular weight (M_n,GPC) was increased versus monomer conversion, and the polydispersities were quite narrow (<1.19), which is the characteristic of controlled polymerization. The chemical structures of these multi‐armed mesogen‐jacketed liquid crystal polymers were confirmed by ¹H NMR. The liquid crystalline behavior of these multi‐armed MJLCPs with arms ranging from two to four was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide‐angle X‐ray diffraction (WAXD). It was found that liquid crystalline phases appeared simply when the number molecular weights (M_n,GPC) of these multi‐armed MJLCPs was higher than a certain critical values, that is, M_n,GPC > 1.87 × 10⁴ g/mol, 1.84 × 10⁴ g/mol, 2.69 × 10⁴ and 3.68 × 10⁴ g/mol, which were initiated by coil difunctional initiator, hard difunctional initiator, trifunctional initiator and tetrafunctional initiator, respectively. All the liquid crystalline phase was found to be stable up to the decomposition temperature of these multi‐armed MJLCPs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3232–3244, 2005     

Well-defined liquid crystal gels from telechelic polymers

Well-defined liquid crystal networks with controlled molecular weight between cross-links and cross-link functionality were prepared by "click" cross-linking of telechelic polymers produced by ring-opening metathesis polymerization (ROMP). The networks readily swell in a small molecule liquid crystal, 5CB, to form LC gels with high swelling ratios. These gels exhibit fast, reversible, and low-threshold optic switching under applied electric fields when they are unconstrained between electrodes. For a given electric field, the LC gels prepared from shorter telechelic polymers showed a reduced degree of switching than their counterparts made from longer polymer strands. The reported approach provides control over important parameters for LC networks, such as the length of the network strands between cross-links, cross-linker functionality, and mesogen density. Therefore, it allows a detailed study of relationships between molecular structure and macroscopic properties of these scientifically and technologically interesting networks.     

Dependence of the biodegradability of carboxymethylcellulose on its supermolecular structure and molecular parameters

It has been established that the resorption of carboxymethylcellulose (CMC) on its implantation into a living organism depends on its molecular mass, degree of substitution, and supermolecular structure. Its mechanism includes both hydrolytic breakdown of the main chain and macrophagal pinocytosis. It has been shown that CMC is absorbed completely and is excreted from the organism without accumulation.A. S. Sadykov Institute of Bioorganic Chemistry, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 62 70 71. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 306–312, March–April, 1995. Original article submitted November 16, 1994.     

Processing and properties of blends with liquid crystal polymers

Experimental data on the processing behavior and on the rheological and mechanical properties of blends with a liquid crystal polymer as one component are presented. The blends with low amounts of LCP show easier processability and lower viscosity than the thermoplastic matrix. The elastic modulus is also improved. The reduction of viscosity has been attributed to the lower pressure entry, due to the formation of fibrils and to the immiscibility of the two phases.     

Synthesis,structure, and properties of chiral liquid crystal monomers and polymers based on menthol

To study structure–mesomorphism relationships of the monomers and polymers based on menthol, four new chiral monomers ( M₁ – M₄ ) and the corresponding homopolymers ( P₁ – P₄ ) with menthyl group were synthesized. Their chemical structures, formula, phase behavior, and thermal stability were characterized by FTIR, ¹H NMR, ¹³C NMR, elemental analyses, differential scanning calorimetry, polarizing optical microscopy, X‐ray diffraction, and thermogravimetric analysis. The selective reflection of light was investigated with ultraviolet/visible spectrometer. The influence of the mesogenic core rigidity, spacer length, and menthyl steric effect on the mesomorphism of M₁ – M₄ and P₁ – P₄ was examined. By inserting a flexible spacer between the mesogenic core and the terminal menthyl groups, four target monomers and polymers could form the expected mesophase. Moreover, their melting temperature (T_m), glass transition temperature (T_g), clearing temperature (T_i), and mesophase range (ΔT) increased with increasing the mesogenic core rigidity; whereas the T_m and T_g decreased, T_i and ΔT increased with an increase of the spacer length. M₁ and M₂ showed monotropic and enantiotropic cholesteric phase, respectively, whereas M₃ and M₄ all revealed chiral smectic C (SmC*), cholesteric and cubic blue phases. In addition, with increasing temperature, the selective reflection of light shifted to the long wavelength region at the SmC* phase range and to the short wavelength region at the cholesteric range, respectively. P₁ and P₂ only showed a smectic A (SmA) phase, whereas P₃ and P₄ exhibited the SmC* and SmA phases. All the obtained polymers had very good thermal stability. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012     

Segmental orientation and mobility of ferroelectric liquid crystal polymers

IR spectroscopy was used to study the orientation and mobility of different molecular segments in a side chain ferroelectric liquid crystalline polymer (FLCP) in the book-shelf geometry. It was directly shown that the tilt angles for the mesogenic units and the spacers are different. The data obtained allowed us to construct a detailed model of segmental orientation in the SC phase for this FLCP. This model is consistent with the 'zigzag' model for tilted smectic phases. The rotational bias of carbonyl bonds is also confirmed and a possible orientation function for the carbonyl group is discussed. Time-resolved step-scan FTIR spectroscopy enabled us to follow the intra- and inter-molecular response of the FLCP to an external electric field with a time resolution of 5 mus. It was detected that mesogenic moiety, spacer and backbone take part in the reorientation process. The time responses of different molecular segments are similar on the time scale of a few hundred microseconds.