Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.

SOLVENT-EXTRACTION OF TERBIUM(III,IV) PERIODATE COMPLEXES WITH QUATERNARY AMINE

The differences between the solvent extraction of Tb(III) and Tb(IV) periodate complexes with quaternary amine were studied carefully for the first time. The effects of extractant concentration, phase ratio, the pH value of stock solution, salting-out agent, extractant form, diluent, and extraction time were comprehensively investigated. Under optimal conditions the separation factor between Tb(IV) and Tb(III) periodate complexes is over 5.5.

Photoreduction of mercuric salt in UV/Fe (III)-oxalate complex system

In this paper, the photochemical reduction process of Hg (II) in aqueous solution containing ferric iron and oxalate (Ox) has been studied. Under the radiation of a low-pressure mercury lamp (lambda = 253.7 nm, 8W), Fe(III)-oxalate complexes undergo photolysis to produce ferrous ions and other organic reductive species, which reduce Hg(II) subsequently. For 0.1 mg/L Hg (II), the photoreduction efficiency is comparatively higher in the solution at pH 5.0 than that over the range of 3.0 similar to 8.0. The photoreduction efficiency of Ho (II) in aqueous solution increases with increasing, initial concentration of ferric ions from 0.02 mmol/L to 0.2 mmol/L and initial concentration of oxalate from 0.96 mmol/L to 4.8 mmol/L and then gradually approaches to a steady state. CH3OH also contributes the reduction of Hg (II). We investigate the increase of the ferric, oxalate and CH3OH concentrations resulting from the increase of reduction efficiency of Hg (II). It can be seen that ferrous ions and other reactive species are reductants of Hg (II), and the reaction product with oxalate is mainly volatile metallic mercury.

The Synthesis and Characterization of a Novel (E,E)-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel (E,E)-dioxime, 5,6:17,18-dibenzo-11,12-(4-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) (H2L), has been synthesized from reaction of (E,E)-dichloroglyoxime (1) with 2,3:14,15-dibenzo 8,9-(4-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane (2). The mononuclear Co(III) complex (4) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex (5) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes (6) and (7) were prepared by reaction of (5) with NiCl2·6H2O and CdCl2·H2O, respectively. In addition, the homotrinuclear Cu(II) complex (8), has also been prepared by the reaction of this dioxime with CuCl2·H2O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1H- and 13C-NMR, IR, and mass spectral data.

Red-light-emitting iridium complexes with hole-transporting 9-arylcarbazole moieties for electrophosphorescence efficiency/color purity trade-off optimizationE

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations

Red-Light-Emitting Iridium Complexes with Hole-Transporting 9-Arylcarbazole Moieties for Electrophosphorescence Efficiency/ Color Purity Trade-off Optimization

The synthesis, structures, photophysics, electrochemistry and electrophosphorescent properties of new red phosphorescent cyclometalated iridium(III) isoquinoline complexes, bearing 9-arylcarbazolyl chromophores, are reported. The functional properties of these red phosphors correlate well with the results of density functional theory calculations. The highest occupied molecular orbital levels of these complexes are raised by the integration of a carbazole unit to the iridium isoquinoline core so that the hole-transporting ability is improved in the resulting complexes relative to those with I-phenylisoquinoline ligands. All of the complexes are highly thermally stable and emit an intense red light at room temperature with relatively short lifetimes that are beneficial for highly efficient organic light-emitting diodes (OLEDs).

Lanthanide-hinged calixarene bicapsules: Discrete hexanuclear Ln(III)/phenanthroline/p-sulfonatocalix[4]arene oligomers (Ln = Gd, Tb)

The dumbbell-like calixarene bicapsule in two novel Ln(III)-C4AS compounds was found to be a hexanuclear Ln(III)/phenanthroline/p-sulfonatocalix[4]arene oligomer. The magnetic and luminescent properties of these compounds were examined.

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

The near-infrared optical properties of an Nd (III) complex and its potential application in electroluminescence

A trivalent neodymium ion (Nd3+) complex Nd(PM)(3)(TP)(2) was synthesized, and its optical properties was studied by introducing Judd-Ofelt theory to calculate the radiative transition rate and the radiative decay time of the F-4(3/2) -> (4)l(J), transitions in this Nd(III) complex. The strong emissions of this complex at near-infrared region were owing to the efficient energy transfer from ligands to center metal ion. The potential application of this complex in NIR electroluminescence was studied by fabricating several devices. The maximum NIR irradiance was obtained as 2.1 mW/m(2) at 16.5 V.

Stabilization of Imidosamarium(III) Cubane by Amidinates

An imidosamarium(III) cubane has been prepared from the reductive cleavage of azobenzene by a divalent samarium bis (amidinate) complex, indicating that the "spectratoe" bis(amidinate) and the resulting imido ligands help to stabilize the cubane framework. The cubane-type imido cluster is a novel unit in lanthanide chemistry.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Two Mn(2)(II)Ln(4)(III) (Ln = Gd, Eu) hexanuclear compounds of p-tert-butylsulfinylcalix[4]arene

Two 3d-4f heterometallic compounds of p-tert-butylsulfinylcalix[4] arene were synthesized by the solvothermal method and characterized by some hinged double-dumbbell-like subunits in which two perpendicular dumbbell entities were constructed by an in-between isosceles triangle Mn(II)Ln(2)(III), and two tail-to-tail calixarene molecules, and hinged by the lanthanide-sulfinyl group bonding. The magnetic properties of the title compounds were examined.

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.