Synthesis, crystal structure, and magnetic properties of {[Cu(oxbe)]Mn(H2O)[Cu(oxbe)(DMF)]}(n)center dot nDMF center dot nH(2)O: From dissymmetrical mononuclear entities to a 3D heterometallic supramolecular coordination polymer

Self-assembly of the building block [Cu(oxbe)](-) with Mn(II) led to a novel coordination polymer {[Cu(oxbe)]Mn(H2O)(Cu(oxbe)(DMF)]}(n).nDMF.nH(2)O, where H(3)oxbe is a new dissymmetrical ligand N-benzoato-N'-(2-aminoethyl)-oxamido and DMF = dimethylformamide. The crystal forms in the triclinic system, space group P(1)over-bar, with a = 9.260(4) angstorm, b = 12.833(5) angstrom, c = 15.274(6) angstrom , alpha = 76.18(3)degrees, beta = 82.7(3)degrees, gamma = 82.31(3)degrees, and Z = 2. The crystal structure of the title complex reveals that the two-dimensional bimetallic layers are constructed of (CuMnII)-Mn-II-Cu-II chains linked together by carboxylate bridge and hydrogen bonds help to produce a novel three-dimensional channel-like structure. The magnetic susceptibility measurements (5-300 K) were analyzed by means of the Hamiltonian (H)over-cap = -2J(S)over-cap (Mn)((S)over-cap(Cu1) + (S)over-cap(Cu2)), leading to J = -17.4 cm(-1).

Hydrothermal syntheses and crystal structures of new cage-like mixed-valent polyoxovanadates

Three new cage-like mixed-valent polyoxovanadates [Ni(1,10'-phen)(3)](2)[V10O26] 1, [Zn(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (2) and [Co(2,2'-biPY)(3)](3)[V15O36Cl](.)3H(2)O (3) have been hydrothermally synthesized for the first time and characterized by elemental analyses, IR, EPR spectra, TG analyses and single crystal X-ray diffraction. The polyoxoanion of I exhibits an interesting empty ellipsoidal [V-2(IV) V-8(V) O-26](4-) 'host' shell, while the oxo vanadium clusters of 2 and 3 possess a spherical [V-8(IV) V-7(V) O36Cl](6-) cage with a Cl- ion encapsulated. The structure-directing role of organic templates (1,10'-phen and 2,2'-bipy) on the formation of the polyoxoanion structures is discussed.

Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex

Copolymerization of carbon dioxide and propylene oxide was carried out employing (RC6H4COO)(3)Y/glycerin/ZnEt2 (R = -H, -CH3, NO2, -OH) ternary catalyst systems. The feature of yttrium carboxylates (ligand, substituent and its position on the aromatic ring) is of great importance in the final copolymerization. Appropriate design of substituent and position of the ligand in benzoate-based yttrium complex can adjust the microstructure of aliphatic polycarbonate in a moderate degree, where the head-to-tail linkage in the copolymer is adjustable from 68.4 to 75.4%. The steric factor of the ligand in the yttrium complex is crucial for the molecular weight distribution of the copolymer, probably due to the fact that the substituent at 2 and 4-position would disturb the coordination or insertion of the monomer, lead the copolymer with broad molecular distribution. Based on the study of ultraviolet-visible spectra of the ternary catalyst in various solvents, it seems that the absorption band at 240-255 nm be closely related to the active species of the rare earth ternary catalysts.

An unusual organic-inorganic chain-like hybrid complex [(CuCl)(2)(o-phen)](infinity) (o-phen=o-phenanthroline)

A novel organic-inorganic hybrid complex [(CuCl)(2) (o-phen)](infinity) 1 (o-phen = o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound I crystallizes in the monoclinic system, space group P2(1)/n, a = 3.7285(7) Angstrom, b = 19.603(4) Angstrom, c = 16.757(3) Angstrom, beta = 95.83(3)degrees, V = 1218.4(4) Angstrom(3), Z = 4, lambda(MoKalpha) = 0.71073 Angstrom (R(F) = 0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60 < θ < 27.48degrees. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu3Cl3] hexagon motifs by, sharing opposite edges. Only Cu(1) sites of the [Cu3Cl3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C-H...Cl hydrogen bonds between o-phen groups and CuCl chains.

Study of electron transfer across the liquid/ice-like matrix interface by scanning electrochemical microscopy

In this work, we report the findings of a study on scanning electrochemical microscopy (SECM) to investigate the interfacial electron-transfer (ET) reaction between the 7,7,8,8-tetracyanoquinodimethane radical anion (TCNQ(.-)) in 1,2-dichloroethane and ferricyanide in an ice-like matrix (a mixture of insulting ice and conductive liquid) under low temperatures. Experimental results indicate that the formed liquid/ice-like matrix interface is superficially similar in electrochemical characteristics to a liquid/liquid interface at temperatures above -20 degreesC. Furthermore, imaging data show that the surface of the ice-like matrix is microscopically flat and physically stable and can be applied as either a conductive or an insulting substrate for SECM studies. Perchlorate ion was selected as the common ion in both phases, the concentrations of which controlled the interfacial potential difference. The effect of perchlorate concentration in the DCE phase on interfacial reactions has been studied in detail. The apparent heterogeneous rate constants for TCNQ(.-) oxidation by Fe(CN)(6)(3-) in another phase under different temperatures have been calculated by a best-fit analysis, where the experimental approach curves are compared with the theoretically derived relationships. Reaction rate data obey Butler-Volmer formulation before and after the freezing point, which is similar to most other known cases of ET reactions at liquid/liquid interfaces. However, there is a sharp change observed for heterogeneous rate constants around the freezing point of the aqueous phase, which reflects the phase transition. At temperatures below -20 degreesC, surface-confined voltammograms for the reduction of ferricyanide were obtained, and the ice-like matrix became an insulating one, which indicates that the aqueous phase is really a frozen phase.

Seed-mediated growth of large, monodisperse core-shell gold-silver nanoparticles with Ag-like optical properties

Large, monodisperse core-shell Au-Ag nanoparticles with Ag-like optical properties have been prepared by the seeding growth method in micellar media.

Electrocatalytic oxidation of NADH by rutin in biomembrane-like films on glassy carbon electrode

Stable lipid film was made by casting dipalmitoylphosphatidylcholine (DPPC) and rutin onto the surface of a glassy carbon (GC) electrode. The electrochemical behavior of rutin in the DPPC film was studied. The modified electrode coated with rutin gave quasi-reversible reduction-oxidation peak on cyclic voltammogram in the phosphate buffer (pH 7.4). The peak current did not decrease apparently after stored at 4 degreesC for 8 hours in refrigerator. This model of biological membrane was used to investigate the oxidation of dihydronicotinamide adenine dinucleotide (NADH) by rutin. Rutin in the film acts as a mediator. The modified electrode shows a great enhancement and the anodic peak potential was reduced by about 220 mV in the oxidation of 5 X 10(-3) mol L-1 NADN compared with that obtained at a bare glassy carbon electrode. (C) 2000 Elsevier Science S.A. All rights reserved.

The single crystal-like banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group

The banded textures in the films of a thermotropic liquid crystalline poly(aryl ether ketone) containing a lateral chloro group have been studied by means of transmission electron microscopy(TEM), electron diffraction(ED) and atomic force microscopy (AFM). The crystallization-induced Landed texture without external shear can be formed when the thin films were annealed at the temperature range(320-330 degrees C) of the liquid crystalline state from the melt, The results show that the banded regions have high orientation of single crystal based on the orthorhombic packing and the growing direction of the Lands is along the b axis of the crystals, This kind of single crystal-like bands is due to the different orientation of the packing molecular chains, The molecular chains of the dark bands in the bright field electron micrograph are perpendicular to the film plane, while the ones of the bright Lands are tilt along the b axis with the tilt angle upto +/-20 degrees.

Synthesis, electrochemistry, and photophysics of a novel binuclear polypyridyl Ru ( II ) complex with an 1,8-adipoylamido-bis(1, 10-phenanthroline-5-yl) ligand

The present paper covers the syntheses of 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl)(bphaa) and its binuclear complex {[(bpy)(2)Ru](2)(bphaa)} (PF6)(4), where bpy is 2,2'-bipyridine. The two novel compounds were confirmed by means of elemental analysis, IR, and LD-MS and H-1 NMR, and H-1 NMR spectra were completely assigned in virtue of H-1-H-1 COSY. chemical behavior of the binuclear Ru (I) complex was obtained using cyclic and voltammetry. Its photophysical property was investigated by electronic absorption, excitation and emission spectra.

Synthesis and thermal polymerization of a novel stilbene-maleimide AB-monomer

A novel AB-monomer, 3-maleimidostilbene (ST-MAI), was synthesized. DSC investigation indicated that the ST-MAI monomer melted at 127 degrees C and thermally polymerized in the temperature range of 180 similar to 300 degrees C. LR investigation on the thermal polymerization processes proved that the thermal polymerization included not only copolymerizaiton between stilbene and maleimide, but also homopolymerization of maleimide. The largest reaction conversion of maleimide and stilbene unit in a ST-MAI monomer was about 82% and 50% respectively. The glass transition temperature of cured ST-MAI resin was 234 degrees C, determined by DSC. The decomposition temperatures for 10% weight loss was above 430 degrees C in both air and nitrogen atmospheres.

Shear-induced spiral-like morphology of a main-chain liquid crystalline poly(aryl ether ketone)

The shear-induced spiral-like morphology of a main-chain thermotropic liquid crystalline poly(aryl ether ketone) is observed and characterized by means of polarizing light microscopy, atomic force microscopy, transmission electron microscopy and electron diffraction techniques. The spiral-like texture is formed during shearing in the temperature range of liquid crystalline to isotropic transition (335-340 degreesC), and dispersed discontinuously in the mosaic matrix. Electron diffraction results indicate that the spiral exhibits orthorhombic lateral packing of the crystals and homeotropic alignment of the molecules. The spiral formation process and possible affecting factors are discussed.

Host-guest-like thiamine-anion complexation in thiaminium bis(tetrafluoroborate)

In the title compound, 3-[(4-amino-2-methyl-5-pyrimidin-1-io)methyl]-5-(2-hydroxyethyl)-4-methylthiazolium(2+) bis(tetrafluoroborate), C12H18N4OS2+. 2BF(4)(-), the divalent thiamine cation (in the F conformation) is associated with BF4- anions via two characteristic bridging interactions between the thiazolium and pyrimidinium rings, i.e. C-H . . . BF4- . . . pyrimidinium and N-H . . . BF4- . . . thiazolium interactions. Thiamine molecules are linked by N-H . . .O hydrogen bonds to form a helical chain structure.

Study of the conductivity and side chain mobility of a comb-like polymer electrolyte using the dynamic mechanical method

Using poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether (PEGME) with different molecular weights as side chains, three comb-like polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the polymer electrolytes possess two glass transitions: alpha -transition and beta -transition, and the temperature dependence of the ionic conductivity shows WLF (Williams-Landel-Ferry) behavior. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T-beta as reference temperature. The values of the WLF parameters (C-1 and C-2) were obtained and were found to be almost independent of the length of the PEGME side chain and the content of Li salt. By reference to T-0 = 50 degreesC. the relation between log tau (c) and c was found to be linear. The master curves are displaced progressively to higher frequencies as the molecular weight of the side chain is increased. The relation between log tau (n) and the molecular weight of the side chain is also linear. (C) 2001 Elsevier Science B.V. All rights reserved.

Co-Cu-Al mixed oxides derived from hydrotalcite-like compound for NO reduction by CO

Various hydrotalcite based catalysts were prepared for catalytic removal of NO (NO reduction by CO). The general formula of hydrotalcite compounds (HTLc) was Co-Cu-Al-HTLc. Precalcination of these materials at 450 degrees C for NO reduction by CO, was necessary for catalytic activity. All catalysts except Co-A1 and Cu-Al have very good activity at lower temperature for NO reduction by CO. All samples were characterized by XRD and BET. The tentative reaction mechanism was also proposed.

Investigation on moleculare and crystal structures of metal complexes with aminopolycarboxylic acids (VII) - Syntheses and structure determination of Na-3[Hg (I) (edta) C1] center dot 6H(2)O

In this paper we describe the moleculare and crystal structures of the Na-3[Hg( II )(edta)Cl] . 6H(2)O (edta=ethylenediamine-N,N,N',N'-tetraacetate). The crystal data are as follows: orthorhombic, a=8. 083 (2) Angstrom , b=13. 870(3) Angstrom , c=38. 617(5) Angstrom , v=4329. 4 (13) Angstrom(3) , Z=8, Dc= 1. 798 g . cm(-3), mu=5. 564 mm(-1), P(000)=2280, R=0. 0317 and R-w=0. 0731 for 3883 unique reflections. In complex, the complex anion [Hg ( II ) (edta)Cl](3-) has a seven-coordination structure like a mono-capped trigonal-prism (C-2v-MTP) in which the edta(4-) acts as a hexadentate ligand with four O atoms and two N atoms and a Cl- caps a quadrilateral face as a seventh ligand. It can be known that the Hg2+ which has a d(10) electronic structure can form a high-coordinate compound with a hexadentate ligand (edta) because it has a big ionic radius.