4-Picoline-N-oxide complexes of rare-earth bromides

In continuation of our work on the effect of the anion on the coordination chemistry of the rare-earth metal ions, we have now extended our studies to 4-picoline-N-oxide (4-Pie NO) complexes of rare-earth bromides. By ohangi~ the method of preparation Harrison and Watsom (1) have prepared two types of Sm(IIl) complexes and three types of Eu(III) complexes of 4-pioollne-N-Oxide in the presence of perchlorate ions. We have isolated two types of pyridine-N-Oxide complexes of rare-earth bromides, also by changing the method of preparation (2). The effect of the change of the preparative method on the composition of the lanthanide complexes is exhibited in the case of other complexes also (3-6). But our attempts to prepare 4-picoline-N-Oxide of rare-earth bromides having different stoichiometries were unsucessful . The composition of the complexes is the same for all the complexes prepared. The results of the physico-chemical studies on these 4-Pic NO complexes of rare-earth bromides are discussed in the present paper.

X-ray crystal structure of a ternary copper(II) vitamin B6 complex, hydroxo(2,2'-bipyridyl)(pyridoxinato) copper(II) monohydrate. A rare example of monodentate coordination of copper(II) by the hydroxyl ion

A ternary metal complex involving Vitamin B6 with the formula [Cu(bipy)(pn) (OH)]H2O (bipy = 2,2'²-bipyridine, PN = anionic pyridoxine) has been synthesized and studied in the solid state by means of spectroscopy and X-ray crystallography. The geometry around copper(II) is distorted square pyramidal, two oxygens from phenolic and 4-(hydroxymethyl) groups of pn, two nitrogens from bipy and an axial OH- ion forming the coordination sphere. In this structure pn exists in a new anionic form with deprotonation of the phenolic group. The structure also provides a rare example of monodentate hydroxyl coordination to copper.

Antipyrine complexes of rare-earth nitrates

Antipyrine complexes of eight rare-earth nitrates of the composition M(C11H12N2O)3 (NO3)3 where M = La, Ce, Pr, Nd, Sm, Gd, Er, and Y, have been prepared by a new, simple method and characterised. The complexes undergo exothermic decomposition at ~3oo°C. Infrared and U.V. spectral studies of the complexes indicate that antipyrine coordinates to metal through oxygen. The nature of the nitrate bonding is discussed in the light of infrared evidence, and conductivity studies in nitromethane and dimethylformamide.

Rare-earth trichloroacetates

The rare-earth trichloroacetates having the formula Ln(Cl3CCOO)3. 3H2O, where Ln = La, Pr, Nd, Sm, Gd or Y, were investigated by conductimetric, cryoscopic and infrared methods. The results suggest a structure in which the acetate anion coordinates to the metal through both the oxygen and the water molecules remain outside the coordination sphere.

Antipyrine complexes of rare earth perchlorates

Rare earth perchlorate-antipyrine (ap) complexes of the formula Ln (ClO4)3.6 ap have been prepared and characterised. Infrared and electronic spectra showed the co-ordination through carbonyl oxygen. Conductivity and molecular weight data indicated a co-ordination number of six for these complexes.

Dimethyl sulphoxide complexes of rare-earth perchlorates

Dimethylsulphoxide (DMSO) complexes of rare-earth perchlorates of the formula M(ClO4)3·n DMSO (M = La, Ce, Pr and Nd, n = 8; M = Sm, Gd and Y, n = 7) have been prepared. I.r. studies indicate co-ordination through oxygen. Cryoscopic and conductivity data show co-ordination number of 7 and 8.

Dimethyl formamide complexes of rare-earth nitrates

Dimethyl formamide complexes of five rare-earth nitrates, M(DMF)4(NO3)3 where M = La, Pr, Nd, Sm or Y have been prepared and their infra-red spectra and conductivities in nitromethane and DMF studied. It is suggested that the co-ordination number of the metal ion in these complexes is nine.

Investigation of activated transport in hole doped rare earth manganites in the high temperature paramagnetic regime

Electronic transport in the high temperature paramagnetic regime of the colossal magnetoresistive oxides, La(1-x)A(x)MnO(3), A=Ca, Sr, Ba, x similar or equal to 0.1-0.3, has been investigated using resistivity measurements. The main motivation for this work is to relook into the actual magnitude of the activation energy for transport in a number of manganites and study its variation as a function of hole doping (x), average A-site cation radius (< r(A)>), cationic disorder (sigma(2)) and strain (epsilon(zz)). We show that contrary to current practice, the description of a single activation energy in this phase is not entirely accurate. Our results clearly reveal a strong dependence of the activation energy on the hole doping as well as disorder. Comparing the results across different substituent species with different < r(A)> reveals the importance of sigma(2) as a metric to qualify any analysis based on (r(A)). (c) 2006 Elsevier Ltd. All rights reserved.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Charge-order driven multiferroic and magneto-dielectric properties of rare earth manganates

Charge-order driven magnetic ferroelectricity is shown to occur in several rare earth manganates of the general formula, Ln(1-x)A(x)MnO(3) (In = rare earth, A = alkaline earth). Charge-ordered manganates exhibit dielectric constant anomalies around the charge-ordering or the antiferromagnetic transition temperature. Magnetic fields have a marked effect on the dielectric properties of these compounds, indicating the presence of coupling between the magnetic and electrical order parameters. Magneto-dielectric properties are retained in small particles of the manganates. The observation of magneto-ferroelectricity in these manganates is in accordance with theoretical predictions.

Piezoresistivity (with uniaxial strain) in nanocrystalline films of rare-earth manganites

We present a study of the piezoresistivity in nanostructured. polycrystalline films of La0.67Ca0.33MnO3 and La0.67Sr0.33MnO3 grown on oxidized Si (100) substrates. We have observed that the hole doped rare-earth manganites, which are well known for being colossal magnetoresistive (CMR) show change in its resistance under uniaxial strain even at room temperature. The piezoresistance was measured at room temperature by bending the Si cantilevers (on which the film is grown) in flexural mode both with compressive and tensile strain. The resistance of the film increases with tensile strain and decreases with compressive strain. A large gauge factor of 15-20 is seen in these films at room temperature.

Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Crystal growth, transport and magnetic properties of rare-earth manganite Pr1-xPbxMnO3

Crystal growth, electrical and magnetic properties are reported for mixed valence manganite Pr1-xPbxMnO3 (x = 0.2, 0.23, and 0.3). The crystals with x = 0.2 and 0.23 are ferromagnetic and insulating, whereas that with x = 0.3 is ferromagnetic below 200 K and shows an insulator-metal transition at 235 K. This composition shows a magnetoresistance of 90% in a field of 5 T. In the paramagnetic region, the temperature dependence of magnetic susceptibility of the crystals follows a Curie-Weiss behavior. The thermal evolution of magnetization in the ferromagnetic phase varies as T-3/2, in accordance with Bloch's law. The spin-stiffness constant D obtained from the Bloch constant is found to increase linearly with x. The magnetization does not reach complete saturation upto a field of 5 T. A possible contribution of the Pr spins to the total magnetic moment is discussed.

Rare-earth chromium citrates as precursors for rare-earth chromites: lanthanum biscitrato chromium(III) dihydrate, La[Cr(C6H5O7)2]·2H

The thermal decomposition of lanthanum biscitrato chromium(III) dihydrate has been studied in static air and dynamic argon atmospheres. The complex decomposes in four steps: dehydration, decomposition of the citrate to an intermediate oxycarbonate, formation of LaCrO4(V) from oxycarbonate, and finally decomposition of LaCrO4(V) to LaCrO3. Formation of LaCrCrO4(V) requires the presence of oxygen The decomposition behaviour of a mechanical mixture of lanthanum citrate hydrate and chromium citrate hydrate was compared with that of the citrato complex. Both the starting material and the intermediates were characterized by X-ray diffraction, IR electronic and ESR spectroscopy, surface area and magnetic susceptibility measurements, as well as by chemical analysis. A scheme is proposed for the decomposition of lanthanum biscitrato chromium(III) dihydrate in air. LaCrO3 can be obtained at temperatures as low as 875 K by isothermal decomposition of the complex.

Investigation of novel cuprates of the TlCa1-xLnxSr2Cu2O7- δ (Ln=rare earth) series showing electron- or hole-superconductivity depending on the composition

Superconductivity in cuprates of the general formula TlCa1-xLnxSr2Cu2O7+ delta has been investigated as a function of Ln and x. Compositions with 0.250.25. Thus, these cuprates exhibit a composition-dependent electron- or hole-superconductivity. In the normal state, most of the members of the series traverse compositionally determined metal-insulator transitions. High-energy spectroscopies show the presence of Cu in the 1+ and 2+ states. The Raman frequency around 525 cm-1 characteristic of the Tl-O2-Cu linkage is sensitive to both Ln and x, indicating a possible involvement in the mechanism of superconductivity.