Metal-insulator transition in Nd1-xEuxNiO 3 compounds

Polycrystalline Nd1-xEuxNiO3 (0≤x≤0.5) compounds were synthesized in order to investigate the character of the metal-insulator (MI) phase transition in this series. Samples were prepared through the sol-gel route and subjected to heat treatments at ∼1000 °C under oxygen pressures as high as 80bar. X-ray diffraction (XRD) and neutron powder diffraction (NPD), electrical resistivity ρ(T), and magnetization M(T) measurements were performed on these compounds. The NPD and XRD results indicated that the samples crystallize in an orthorhombic distorted perovskite structure, space group Pbnm. The analysis of the structural parameters revealed a sudden and small expansion of ∼0.2% of the unit cell volume when electronic localization occurs. This expansion was attributed to a small increase of ∼0.003 of the average Ni-O distance and a simultaneous decrease of ∼-0.5° of the Ni-O-Ni superexchange angle. The ρ(T) measurements revealed a MI transition occurring at temperatures ranging from TMI∼193 to 336K for samples with x ≤ 0 and 0.50, respectively. These measurements also show a large thermal hysteresis in NdNiO3 during heating and cooling processes, suggesting a first-order character of the phase transition at TMI. The width of this thermal hysteresis was found to decrease appreciably for the sample Nd 0.7Eu0.3NiO3. The results indicate that cation disorder associated with increasing substitution of Nd by Eu is responsible for changing the first-order character of the transition in NdNiO3. © 2006 IOP Publishing Ltd.

Synthesis of isotactic polystyrene with a rare-earth catalyst

Polymerization of styrene with the neodymium phosphonate Nd(P-507)/H2O/Al(i-Bu)(3) catalytic system has been examined. The polymer obtained was separated into a soluble and an insoluble fraction by 2-butanone extraction. C-13-NMR spectra indicate that the insoluble fraction is isotactic polystyrene and the soluble one is syndiotactic-rich atactic polystyrene. The polymerization features are described and discussed. The optimum conditions for the polymerization are as follows: [Nd] = (3.5-5.0) x 10(-2) mol/L; [styrene] = 5 mol/L; [Al]/[Nd] = 6-8 mol/mol; [H2O]/[Al] = 0.05-0.08 mol/mol; polymerization temperature around 70 degrees C. The percent yield of isotactic polystyrene (TY) is markedly affected by catalyst aging temperature. With increase of the aging temperature from 40 to 70 degrees C, TY increases from 9% to 48%. Using AlEt3 and Al(i-Bu)(2)H instead of Al(i-Bu)(3) decreases the yield of isotactic polystyrene. Different neodymium compounds give the following activity order: Nd(P-507)(3) > Nd(P-204)(3) > Nd(OPri)(3) > NdCl3 + C2HF5OH > Nd(naph)(3). With Nd(naph)(3) as catalyst, only atactic polystyrene is obtained. (C) 1998 John Wiley & Sons, Inc.

Room temperature visible/infrared emission and energy transfer in Nd3+-based organic/inorganic hybrids

The photoluminescence features and the energy transfer processes of Nd3+-based siloxanepoly(oxyethylene) hybrids are reported. The host matrix of these materials, classed as di-ureasils, is formed by a siloxane backbone covalently bonded to polyether chains of two molecular weights by means of urea cross-links. The room-temperature photoluminescence spectra of these xerogels show a wide broad purple-blue-green band (350-570 nm), associated with the emitting centres of the di-ureasil host, and the typical near infrared emission of Nd3+ (700-1400 nm), assigned to the 4F3/2 → 4I9/2,11/2,13/2 transitions. Self-absorptions in the visible range, resonant with intra-4f3 transitions, indicate the existence of an energy conversion mechanism of visible di-ureasil emission into near infrared Nd3+ luminescence. The existence of energy transfer between the di-ureasil's emitting centres and the Nd3+ ions is demonstrated calculating the lifetimes of these emitting centres. The efficiency of that energy transfer changes both with the polymer molecular weight and the Nd3+ concentration.

Síntese, caracterização e estudo termoanalítico dos mandelatos de lantanídeos(III), exceto o promécio, e de ítrio(III) no estado sólido

Pós-graduação em Química - IQ

Lanthanum, praseodymium and neodymium chloroacetates

The monochloroacetates of lanthanum, praseodymium and neodymium of the composition M(ClCH2COO)3·2H2O have been prepared and characterised. The compounds behave as non-electrolytes in dimethylformamide. The infrared spectra are consistent with bidentate coordination of the carboxylate group and show the presence of two types of water molecules, coordinated, and free. With six oxygen atoms from the three acetato groups and one from the water bonded to the metal, a coordination number of seven has been assigned to the rare earths in these compounds. On pyrolysis, the chloroacetates lose water at ~130 °C and yield the oxychlorides at ~500 °C. The X-ray powder patterns of the chloroacetates have been indexed for the monoclinic system, with four molecules per unit cell.

Mitochondrial selectivity and remarkable photocytotoxicity of a ferrocenyl neodymium(III) complex of terpyridine and curcumin in cancer cells

A series of four novel neodymium(III) complexes of the formulation Nd(R-tpy)(O-O)(NO3)(2)] (1-4), where R-tpy is 4'-phenyl-2,2': 6', 2''-terpyridine (Ph-tpy; 1, 2) and 4'-ferrocenyl-2,2': 6', 2''-terpyridine (Fc-tpy; 3, 4); O-O is the conjugate base of acetylacetone (Hacac; 1, 3) or curcumin (Hcurc; 2, 4), are synthesized and characterized. The single crystal structure of 1 shows that the complex is a discrete mononuclear species with the Nd(III) centre in a nine coordinate environment provided by a set of O6N3 donor atoms. Complexes 1 and 3 having the simple acac ligand are prepared as control compounds. Complex 4, possessing an appended ferrocenyl (Fc) and the curcumin moiety, is remarkably photocytotoxic to HeLa and MCF-7 cancer cells in visible light giving respective IC50 values of 0.7 mu M and 2.1 mu M while being significantly less toxic to MCF-10A normal cells (IC50 = 34 mu M) and in the dark (IC50 > 50 mu M). The phenyl appended complex 2, lacking a ferrocenyl moiety, is significantly less toxic to both the cell lines when compared with 4. Complexes 1 and 3, lacking the photoactive curcumin moiety, do not show any apparent toxicity both in light and in the dark. The cell death is apoptotic in nature and is mediated by the light-induced formation of reactive oxygen species (ROS). Fluorescence imaging experiment with HeLa cells reveals mitochondrial accumulation of complex 4 within 4 h of incubation. The complexes bind to calf thymus (ct) DNA with moderate affinity giving K-b values in the range of 10(4)-10(5) M-1. The curcumin complexes 2 and 4 cleave plasmid supercoiled DNA to its nicked circular form in visible light via O-1(2) and (OH)-O-center dot pathways. The presence of the ferrocenyl moiety is likely to be responsible for the enhanced cellular uptake and photocytotoxicity of complex 4. Thus, the mitochondria targeting complex 4, being remarkably cytotoxic in light but non-toxic in the dark and to normal cells, is a potential candidate for photochemotherapeutic applications.

Phase stability and thermophysical properties of neodymium cerium composite oxide

Nd2CexO3+2x (x = 2.25, 2.5, 2.75, 3.0) were synthesized by solid-state reaction, and their phase stabilities and thermophysical properties were investigated. The X-ray diffraction (XRD) results indicated that Nd2CexO3+2x with fluorite structure were stable after long-term annealing at 1673 K. They have higher thermal expansion coefficients (TECs) than yttria-stabilized zirconia (YSZ) which is the typical thermal barrier coating (TBC) material, especially the thermal expansion as a function of temperature is parallel to that of the nickel-based superalloy.

SYNTHESIS, SOLUTION DYNAMICS AND X-RAY CRYSTAL-STRUCTURES OF NEODYMIUM-YLIDE COMPLEXES, [(C(5)H(4)R)(3)NDCH2P(ME)PH(2)] (R=H, BU(T))

The interaction of [(C(5)H(4)R)(2)NdCl.2LiCl] (R = H, Bu(t)) with one equivalent of Li[(CH2)(CH2)PPh(2)] in refluxing tetrahydrofuran gave the purplish-blue complex [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] in 50% yield. The compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. Variable temperature P-31{H-1} NMR spectroscopy indicated the existence of the following equilibrium: [(C(5)H(4)R)(3)NdCH2P(Me)Ph(2)] + THF reversible arrow (C(5)H(4)R)(3)Nd(THF) + CH2=P(Me)Ph(2). At room temperature, the exchange between the coordinated and free ylide ligand is slow on the NMR time scale.

SYNTHESIS, STRUCTURE AND SPECTRA PROPERTIES OF THE NEODYMIUM MOLYBDOGERMANATE HETEROPOLY COMPLEX

K7H6[Nd(GeMo11O39)2].18H2O was first synthesized and the crystal structure was determined. Crystal structure data are as follows: monolinic, space group P2(1)/n, a = 1.7095(4), b = 2.6895(3), c = 2.1214(5) nm, beta = 103.11 (2)-degrees, V = 9.4994(3) nm3, Z = 4, D(m) = 3.14g/cm3, D(c) = 3.05g/cm3, mu(MoK-alpha) = 43.7 cm-1. Experimental evidence and theoretical foundation of the method inferring the molecule structure of heteropoly compounds using their IR spectra were gaved by studying IR spectra properties of the complex with results of structural analysis. Electronic spectra prove that 4f-obital of Nd3+ take part in bonding in the complex.

PREPARATION AND MOLECULAR-STRUCTURE OF METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)NEODYMIUM AND METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)GADOLINIUM

Bis(t-butylcyclopentadienyl)lanthanide chloride (Ln = Nd or Gd) reacts with one equivalent of methyllithium in ether/tetrahydrofuran to give the complex [(C5H4tBu)2LnCH3]2 (Ln = Nd or Gd). The structure of [(C5H4tBu)2NdCH3]2 has been determined by X-ray analysis. The crystals are monoclinic of space group Cm with a = 9.538(2), b = 23.298(4), c = 9.505(3) angstrom, beta = 119.53(2)-degrees, V = 1828.0(7) angstrom 3, D(calc.) = 1.458 g/cm3 and Z = 2 for the dimer. The two (C5H4tBu)2Nd units in the dimer are connected by asymmetrical methyl bridges with independent Nd-C bond lengths of 2.70(2) and 2.53(2) angstrom and Nd-C-Nd angles of 94.7(9) and 87.3(6)-degrees.

Energy upconversion luminescence in neodymium-doped tellurite glass

Infrared-to-visible upconversion luminescence emission in Nd3+-doped 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) tellurite glasses under cw excitation around 800 nm is investigated. Blue (430, and 475 nm), green (5 0 nm) and yellow-orange (590 nm) energy upconversion emission owing to the P-2(1/2) --> I-4(j) (j=9/2, 11/2, 13/2 and 15/2) transitions of the Nd3+ ions, respectively, was recorded. The dependence of the upconversion intensity upon the excitation wavelength and pump power is also studied. The upconversion excitation mechanism responsible for the observed emission signals is attributed to stepwise multiphoton absorption. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Energy-transfer frequency upconversion in neodymium-sensitized praseodymium-doped PbGeO3-PbF2-CdF2 glass excited at 810 nm

Visible frequency upconversion emission through resonant energy-transfer involving neodymium and praseodymium ions in PbGeO3-PbF2-CdF2 glass excited by a semiconductor laser at 8 10 nm is investigated. Luminescence emission centered around 485, 530, 610, and 645 nm, which correspond to the P-3(0) -> H-3(4), P-3(1) + I-1(6) -> H-3(5), P-3(0) -> H-3(6) and P-1(0) -> F-3(2) transitions of praseodymium ions, respectively, are observed. The upconversion excitation of the Pr3+ ions excited-state emitting levels was accomplished by means of an ion-pair interaction involving ground-state absorption, multiphonon relaxation, and excited-state absorption of pump photons at 8 10 nm by the Nd3+ (I-4(9/2) -> H-2(9/2), F-4(5/2); F-4(3/2) -> P-2(1/2)) and direct energy-transfer to Pr3+ ((4)G(11/2) + K-2(11/2), H-3(4) -> I-4(9/2), P-3(1) + I-1(6)). The dependence of the upconversion emission intensity upon the excitation power, and neodymium concentration are also examined. (c) 2004 Elsevier B.V. All rights reserved.

Polysulfurated aromatic compounds: preparation and photophysical properties

The aim of this thesis was the synthesis and photophysical characterization of some new polysulfurated aromatic compounds: this class of molecules can offer intriguing properties, potentially useful for the construction of new materials for optoelectronic devices. Two main families of compounds have been synthesized: the first is represented by a series of small molecular asterisks, with peripheral aromatic units, showing luminescence in solid phase or in highly rigid conditions. All compounds with peripheral substituents display an AIE behavior (Aggregation Induced Emission) with radiative deactivation of the triplet states. Taking inspiration from these smaller asterisks, a larger molecule with the same geometry has been designed, decorated with terpyridyl moieties as the outermost units: this compound shows great affinity for the coordination of several transition metal ions, changing luminescence properties after the interaction with zinc ions. With the same intentions, a tetrasulfurated pyrene-core molecule with terpyridyl external units has been synthesized and isolated: this ligand exhibits good coordination capabilities towards transition metal ions, giving rise to luminescent nanoaggregates upon addition of zinc(II), characterized by DLS and AFM microscopy. In addition a NIR emission is recorded after coordination of neodymium(III), showing evidence of an intramolecular energy transfer process.