Hydrothermal synthesis and crystal structure of a layered inner-tunnel compound [(CuI)(2)(o-phen)(2)]

A layered inner-tunnel supramolecular compound 1, [(CuI)(2)(o-phen)(2)], was hydrothermally synthesized and structurally characterized by X-ray crystal diffraction. It crystallizes in triclinic system, space group P (1) over bar with a=0.7759(2) nm, b=0.9070(2) rim, c=0.91894(10) rim, alpha=96.306(14)degrees, beta=104.567(16)degrees, gamma=109.421(19)degrees, V=0.5768(2) nm(3), Z=1, R=0.0348, omegaR=0.0920.

Carbon ceramic electrodes bulk-modified with nanoparticles of ferrocenebutyrate-intercalated Mg-Al layered double hydroxide

Ferrocenebutyrate-intercalated layered double hydroxide (FcLDH) was prepared by the coprecipitation method and characterized by PXRD, FTIR, TEM and elemental analysis. FcLDH nanoparticles in deionized water were deposited onto the surface of graphite powder to yield graphite powder-supported FcLDH, which was subsequently dispersed into methyltrimethoxysilane-derived gels to fabricate surface-renewable, stable, rigid carbon ceramic electrodes containing the electroactive ferrocenyl group. Cyclic voltammetric study revealed that peak currents of the FcLDH-modified electrode were diffusion-con trolled in 0.1 mol l(-1) KCl aqueous solution. In addition, the formal potential of the modified electrode is related to the activity of chloride ion with a Nernst slope of 56 mV per decade.

Gas transport properties of a series of cardo polyarylethers

Gas transport of H-2, CO2, O-2, N-2, and CH4 in a series of cardo polyarylethers were examined over a temperature range of 30 similar to 100 degreesC. These polymers include three poly(aryletherketone)s, two poly(arylethersulfone)s, and one poly(aryletherketoneketone). It was found that the large length/diameter ratio of the polymer repeat unit for cardo polyaryletherketoneketone (PEKK-C) and strong intermolecular interaction in hydrogen-bonded polyarylethersulfone (PES-H) and hydrogen-bonded polyaryletherketone (PEK-H) resulted in a considerable increase in gas permselectivity. Alkyl-substituted polyaryletherketone (PEK-A), bearing a pendant bulky propyl group on the cardo ring, simultaneously exhibited 62.5% higher H-2 permeability and 59.8% higher H-2/N-2 permselectivity than unmodified poly(aryletherketone) (PEK-C). The causes of the trend were interpreted in terms of chain packing density, segmental motion ability, steric factor, and intermolecular interaction of polymers, together with gas kinetic diameter and critical temperature data.

Structural phase transition in the layered perovskite compound BaTb2Mn2O7

A distorted layered perovskite compound BaTb2Mn2O7 was synthesized by the solid state reaction in pure argon. There is a structural phase transition in the BaTb2Mn2O7 compound. The phase transition was characterized by the DSC and high temperature Xray diffraction. The heat capacity of BaTb2Mn2O7 was calculated. The thermal anomaly corresponding to the phase transition was observed at about 740K. The lattice parameters were calculated by the CELL program for BaTb2Mn2O7, It has Tb-type orthorhombic symmetry with a = 0.3908 nm, b = 0.3866 nm, c = 2.0163 nm, and space group Immm at room temperature. With the increase of temperature, the lattice parameters gradually increase until 673K. From 723K to 973K, the compound translates to tetragonal with a = 0.39078 nm, c = 2.0277 nm and S.G. I4/mmm. This result is fairly in accordance with that of heat capacity.

Preparation, characterization and photophysical properties of layered zirconium bis(monohydrogenphosphate) intercalated with rare earth complexes

Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (alpha -ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)(2). 2PMA (alpha -ZrP . 2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)(3)phen (AA: acetylacetone) intercalated into alpha -ZrP . 2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.

Synthesis and properties of three novel series of monomers containing para-methoxyazobenzene as the mesogenic group

Three novel series of monomers, namely n-1-bromo-[4-(4-methoxyphenylazo)phenyloxy]-alkanes (Bn, n = 3, 6, 10), n-[4-(4-methoxyphenylazo) phenyloxy]alkyloxy-4-methoxybenzene (Cn, n = 3, 6, 10) and n-[4-(4-methoxyphenylazo)phenyloxyl]alkyloxy-[4-methoxy-2,5-bis-(chloromethyl)] benzene (Dn, n = 3, 6, 10) were synthesized and characterized with FTIR, H-1 NMR, UV-visible and fluorescence spectroscopy. Their thermal behaviour was studied by different scanning calorimetry and polarizing optical microscopy. The results show that B3, B6 and C6 exhibit monotropic nematic liquid crystalline behaviour.

Preparation and characterization of layered compound zirconium bis(monohydrogenphosphate)intercalated with rare earth complex

Layered compound zirconium bis(monohydrogenphosphate)(alpha-ZrP) intercalated with rare earth complex Eu(DBM)(3)phen was prepared. The pre-intercalation of p-methoxyaniline into alpha-ZrP makes the interlayer separation large enough to exchange PMA with europium complex, thus, the luminescent assembly was prepared. This was confirmed by X-ray diffraction, UV-visible spectra and elemental analysis. The fluorescence spectra and lifetime of the assembly were also presented.

Gas and water vapor transport through a series of novel poly(aryl ether sulfone) membranes

The permeation behavior of water vapor, H-2, CO2, O-2, N-2, and CH4 gases in a series of novel poly(aryl ether sulfone)s has been examined over a temperature range of 30-100 degreesC. These polymers include four alkyl-substituted cardo poly(aryl ether sulfone)s and four intermolecular interaction enhanced poly(aryl ether sulfone)s. Their water vapor and gas transport properties were compared to the unmodified cardo poly(aryl ether sulfone) (PES-C). It was found that the bulky alkyl substituents on the phenylene rings were advantageous for gas permeability, while the intermolecular hydrogen bonds and ionic bonds resulted in a considerable increase in gas permselectivity. The causes of the trend were interpreted according to free volume, interchain distance, and glass transition temperature, together with the respective contribution of gas solubility and diffusivity to the overall permeability. Of interest was the observation that IMPES-L, which simultaneously bears bulky isopropyl substituent and pendant carboxylic groups, displayed 377% higher O-2 permeability and 5.3% higher O-2/N-2 permselectivity than PES-C. Furthermore, sodium salt form PES-Na+ and potassium salt form PES-K+ exhibited water vapor permeability twice as high as PES-C and H2O/N-2 selectivity in 10(5) order of magnitude.

Hydrothermal synthesis and crystal structure of a novel layered compound [Ni(C10H8N2)(2)V3O8.5]

A novel layered compound, [Ni(C10H8N2)(2)V3O8.5], was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 1.551 8(3) nm, b = 1.476 1(3) nm, c = 1.048 3(2) nm, beta = 92.02(3), V = 2.399 8(8) nm(3), Z = 4, R = 0. 046 7, wR(2) = 0. 085 9.

Formation of mesophase mono-domains and micro-structures in thin films of a series of copolyethers containing both odd-numbered methylene units

The structural and morphological evolution of mono-domains in thin films has been investigated for a series of liquid crystalline (LC) copolyethers. The copolyethers studied were synthesized by the reaction of 1-(4-hydroxy-4 ' -biphenylyl)-2-(4-hydroxyl-phenyl)propane (TPP) with 1,7-dibromoheptane and 1,11-undecane at different compositions (coTPPs-7/11). In contrast to the solution-cast thin films without annealing, which exhibit the isotropic homogeneous molecular orientation, mono-domains with a homeotropic alignment were found in coTPP-7/11(5/5) after the thin films were annealed in the high-temperature columnar phase (Phi '). Similar to the nucleation process in polymer crystallization, transmission electron microscopic observations show that small mono-domains appear in the initial stage of annealing, where molecules form a uniaxial in-plane chain orientation. With increasing annealing time, the molecular orientation gradually became tilted with respect to the substrate surface, and finally, a uniaxial homeotropic molecular orientation was achieved after a prolonged annealing time. The lateral size of mono-domains was found to increase continuously with annealing time and grew into a circular shape, indicating an isotropic lateral growth scheme which implies a hexagonal molecular packing proved by the electron diffraction experiments.

Study on a series of main-chain liquid-crystalline ionomers containing sulfonate groups

A series of main-chain Liquid-crystalline ionomers containing sulfonate groups pendant on the polymer backbone were synthesized by an interfacial condensation reaction of 4,4'-dihydroxy-alpha,alpha'-dimethyl benzalazine, a mesogenic monomer, with brilliant yellow (BY), a sulfonate-containing monomer, and a 1/9 mixture of terephthaloyl and sebacoyl dichloride. The structures of the polymers were characterized by LR and UV spectroscopies. DSC and thermogravimetric analysis were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by a polarized optical microscope, DSC, and wide-angle X-ray diffraction. The ionomers were thermally stable to about 310 degreesC. They were thermotropic liquid-crystalline polymers (LCPs) with high mesomorphic-phase transition temperatures and exhibited broad nematic mesogenic regions of 160-170 degreesC, and they were lyotropic LCPs with willowy leaf-shaped textures in sulfuric acid. However, the thermotropic liquid-crystalline properties were somewhat weakened because the concentration of BY was more than 8%. The inherent viscosity in N-methyl-2-pyrrolidone suggested that intramolecular associations of sulfonate groups occurred at low concentration, and intermolecular associations predominated at higher concentration. (C) 2001 John Wiley & Sons, Inc.

Synthesis and characterization of a series of high sulfonated poly(ether ether ketone)s

A series of high sulfonated poly(ether ether ketone)s were prepared by copolymerization of sodium 5,5 ' -carbonylbis (2-fluorobenzenesulfonate)(2),4,4 ' -difluorobenzophenone (1) and bisphenol A(3) in the presence of potassium carbonate in dimethylsulfoxide. The copolymers were characterized by IR and DSC, The influence of degree of sulfonation on the properties of copolymers, such as component, thermal stability, solubility and filming ability, was studied.

Synthesis and characterization of a new layered zinc phosphate: (C3H4N2)(3)Zn-4(HPO4)(PO4)(2) with imidazole coordinating to Zn atoms

A new two-dimensional hybrid zinc phosphate with electro-neutral open-framework has been hydrothermally synthesized by using imidazole as a structure-directing agent, whose structure is characterized with 3-, 4-, 5, and 12-ring layers and coordination bonds between imidazole groups and zinc atoms, resulting in primary building units of ZnO2N2 and ZnO3N.

Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 7. Phase structures in a series of copolyethers containing odd and even numbers of methylene units of different compositions

A series of liquid crystalline copolyethers have been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,12-dibromododecene [coTPPs(7/12)], which represents copolyethers containing both odd and even numbers of methylene units. The molar ratio of odd to even methylene units in this series ranges from 1/9 to 9/1. The coTPPs(7/12) exhibit multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. For all these thermal transitions, a small undercooling and superheating dependence is observed upon cooling and heating at different rates. Three types of phase behaviors can be classified in coTPPs(7/12) on the basis of the structural analyses by wide-angle X-ray diffraction on powder and fiber samples and by electron diffraction experiments in transmission electron microscopy. At room temperature, highly ordered smectic and smectic crystal (SC) phases are identified in coTPPs(7/12: 1/9 and 2/8), which is similar to the homopolymer TPP(m = 12). The coTPPs(7/12: 3/7, 4/6, and 5/5) possess a hexagonal columnar (Phi(H)) phase in which the molecular and columnar axes are parallel to the fiber direction and perpendicular to the hexagonal lateral packing. The coTPPs(7/12: 6/4, 7/3, and 8/2) possess a tilted hexagonal columnar (Phi(TH)) phase with a single tilt angle which increases with the increasing composition of the seven-numbered methylene units. However, in coTPP(7/12: 9/1), a Phi(TH) phase with multiple tilt angles is found. Upon heating, phase structures in most coTPPs(7/12) involving the columnar phases enter directly into the nematic (N) phase, while the coTPP(7/12: 1/9) exhibits a highly ordered smectic F (S-F) phase before it reaches the N phase. One exception is found in coTPP(7/12: 2/8), wherein the transformation from the S-F to Phi(H) occurs prior to the N phase. Combining the copolymer phase behaviors observed with the corresponding homopolymers TPP(n = 7) and TPP(m = 12), a phase diagram describing transition temperatures with respect to the composition can be constructed.

Investigation of a series of synthetic cationic porphyrins using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to study a series of synthetic cationic porphyrins as the perchlorate and bromide salts. This work presents the analytical results for the porphyrins obtained using 2,5-dihydroxybenzoic acid (DHB) and 1,8,9-anthratriol as matrices. The selective use of matrix affects ion formation from these porphyrins. By using DHB as the matrix, we not only observed [M - nCIO(4)](+) (n = 1-4) ions, but also obtained [2M - nCIO(4)](+) (n = 2-7) ions from the synthetic cationic porphyrins. The space volume of the side chains (R groups) and the nature of the anions (Br- or CIO4-) affected the relative importance of monomeric and dimeric ions of the porphyrin. The possible mechanisms of desorption and ionization of these cationic porphyrins were also considered in this study. MALDI-TOFMS proved to be a very useful method for obtaining structural information on these synthetic cationic porphyrins. Copyright (C) 1999 John Whey & Sons, Ltd.