Mean-field results of the multiple-band extended Hubbard model for the square-planar CuO2 lattice

We obtain metal-insulator phase diagrams at half-filling for the five-band extended Hubbard model of the square-planar CuO2 lattice treated within a Hartree-Fock mean-field approximation, allowing for spiral spin-density waves. We indicate the existence of an insulating phase (covalent insulator) characterized by strong covalency effects, not identified in the earlier Zaanen-Sawatzky-Allen phase diagram. While the insulating phase is always antiferromagnetic, we also obtain an antiferromagnetic metallic phase for a certain range of interaction parameters. Performing a nonperturbative calculation of J(eff), the in-plane antiferromagnetic interaction is presented as a function of the parameters in the model. We also calculate the band gap and magnetic moments at various sites and discuss critically the contrasting interpretation of the electronic structure of high-T(c) materials arising from photoemission and neutron-scattering experiments.

Synthesis, structure and redox properties of (?-oxo)bis(?-carboxylato)diruthenium(III) complexes containing three different terminal ligands

Blue coloured, unstable, essentially diamagnetic and non-electrolytic diruthenium(III) complexes of the formation [Ru2O(O2CR)4(en)2(PPh3)2] were prepared by reacting [Ru2O(O2CR)4(PPh3)2] with 1,2-diaminoethane (en) in CH2Cl2 (R = C6H4-p-X; X = H, Me and OMe). The molecular structure of the complexes is proposed as [{(?1-O2CR)(?1-en)(PPH3)Ru}2(?-O)(?-O2CR)2] based on the 1H NMR spectral data. The electronic spectra of the complexes display a band near 569 nm with a shoulder at 630 nm. In CH2Cl2-0.1 M [Bun4N]ClO4, the complexes exhibit redox couples Ru2III,III/Ru2III,IV and Ru2III,IV/Ru2IV,IV near 0.1 and 1.2 V (vs SCE), respectively. The potentials are the lowest among diruthenium(III) complexes with a similar core structure.

Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

Substrate-dependent structure, microstructure, composition and properties of nanostructured TiN films

Titanium nitride films of a thickness of similar to 1.5 mu m were deposited on amorphous and crystalline substrates by DC reactive magnetron sputtering at ambient temperature with 100% nitrogen in the sputter gas. The growth of nanostructured, i.e. crystalline nano-grain sized, films at ambient temperature is demonstrated. The microstructure of the films grown on crystalline substrates reveals a larger grain size/crystallite size than that of the films deposited on amorphous substrates. Specular reflectance measurements on films deposited on different substrates indicate that the position of the Ti-N 2s band at 2.33 eV is substrate-dependent, indicating substrate-mediated stoichiometry. This clearly demonstrates that not only structure and microstructure, but also chemical composition of the films is substrate-influenced. The films deposited on amorphous substrates display lower hardness and modulus values than the films deposited on crystalline substrates, with the highest value of hardness being 19 GPa on a lanthanum aluminate substrate. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis, x-ray structure and redox properties of [Ru2(?-O) (?-O2CMe)2(Me2NCH2CH2NH2)2(PPh3)2](ClO4)2

The title complex has been prepared from a reaction of [Ru2O(O22CMe)2 (MeCN)4(PPH3)2](ClO4)2 with N,N-dimethyl-1,2-diaminoethane (dmen) in MeOH. The crystal structure of [Ru2O(O2CMe)2(dmen)2(PPh3)2](ClO4)2.MeOH shows the presence of a [Ru2(mu-O)(mu-O2CMe)2]2+ core. The terminal ligands on each metal are a PPh3 and a bidentate chelating dmen. The Ru-Ru distance and Ru-O-Ru angle in the core are 3.271(2) angstrom and 120.9(4)-degrees. The more electron-donating site of the dmen ligand is bonded at the terminal sites trans to the mu-oxo ligand. The complex displays a visible absorption band at 566 nm (epsilon, 6960 M-1 cm-1) in MeCN and undergoes a nearly reversible one-electron oxidation at 1.02 V and an irreversible reduction at -0.52 V (vs SCE) in MeCN-0.1 M [NBu4n](ClO4).

Ab initio studies of the structure and vibrational spectra of methyl isocyanide-borane and acetonitrile-borane

The SCF/DZP and MP2/DZP methods of ab initio quantum chemistry have been utilized to study the structure, vibrational spectra, binding energy, and barrier to internal rotation of methyl isocyanide-borane and acetonitrile-borane adducts. The eclipsed conformation of the complexes was predicted to be a minimum, and the staggered form is a transition state with a barrier height of about 10 cal/mol. The vibrational analyses of CH3NC-BH3 and CH3CN-BH3 and several of their isotopomers have been carried out by the GF matrix method. Computations have also been carried out for free CH3NC and CH3CN in order to investigate the changes in CH3NC and CH3CN as a result of their complex formation with BH3. To obtain an acceptable set of force constants, a recently proposed procedure ''RECOVES'' has been utilized. The increase in the N=C/C=N stretching force constant of CH3NC/CH3CN on adduct formation is interpreted with the help of Parr and Borkman's model. The binding energies for the two adducts have been determined taking basis set superposition error (BSSE) into consideration. The effect of the BSSE on structure, dipole moment, and vibrational frequencies of CH3CN and CH3NC is also evaluated. The predicted infrared band intensities for the two complexes are in good agreement with the experimentally observed features, and they have been utilized in the assignment of vibrational frequencies.

Preparation, structure, and properties of strontium-doped lanthanum chromites: La1−xSrxCrO3

Strontium-doped lanthanum chromites, La1−xSrxCrO3, have been synthesised to investigate the effect of strontium doping on the stability and physico-chemical characteristics of the perovskite LaCrO3. Both microscopic and X-ray examinations show that the materials exist as single phase perovskite structure for all compositions up to 50 mole% strontium substitution. The materials have been further characterized by infrared and electron paramagnetic resonance spectra. These materials show a good sinterability even in air at 1773 K. Electrical conductivity of thse perovskites has been measured as a function of temperature. Electrical conductivity has been found to be a maximum at x=0.2. The observed electrical and magnetic properties are consistent with activated polaron transport as the mechanism for electrical conduction in these materials.

Intraloop and Interloop Interactions in the Folded-G Quartet Structure of Oxytricha Telomeric Sesquence

The antiparallel intramolecular G quartet structure for the 3.5 copy Oxytricha telomeric sequence d(G(4)T(4))(3)G4 has been established using a combination of spectroscopic and chemical probing methods. In the presence of Naf ions, this sequence exhibits a circular dichroism spectrum with a positive band at 295 nm and a negative band around 265 nm, characteristic of an antiparallel G quartet structure. Further, we show that d(G(4)T(4))(3)G(4) adopts an antiparallel intramolecular G quartet structure even in K+ unlike d(G(4)T(4)G(4)). KMnO4 probing experiments indicated the existence of intra and interloop interactions in the Na+ induced structure. We have found that K+ not only increases the thermal stability of,G quartet structure but also binds to the loop region and disrupts stacking and interloop interactions. Biological consequences of such cation-dependent conformational micro-heterogeneity in the loop region of G quartet structures is also discussed.

Effect of SDS on human hair: Study on the molecular structure and morphology

This paper presents a model study to understand the effect of surfactants on the physicochemical properties of human hair. FT-IR ATR spectroscopy has been employed to understand the chemical changes induced by sodium dodecyl sulfate (SDS) on human scalp hair. In particular, the SDS induced changes in the secondary structure of protein present in the outer protective layer of hair, i.e. cuticle, have been investigated. Conformational changes in the secondary structure of protein were studied by curve fitting of the amide I band after every phase of SDS treatment. It has been found that SDS brings rearrangements in the protein backbone conformations by transforming beta-sheet structure to random coil and beta-turn. Additionally, AFM and SEM studies were carried out to understand the morphological changes induced on the hair surface. SEM and AFM images demonstrated the rupture and partial erosion of cuticle sublayers.

Magneto-structural correlation in (mu-alkoxo/hydroxo)(mu-carboxylato)dicopper(II) systems: Synthesis, X-ray structure and magnetic properties of aquo(mu-hydroxo) (mu-arylcarboxylato)bis(N,N,N ',N '-tetramethylethane-1,2-diamine)dicopper(II) diperchlorate

Asymmetrically dibridged dicopper(II) complexes, [Cu-2(OH)(O2CC6H4-p-Me)(tmen)(2)(H2O)](ClO4)(2) (1) and [Cu-2(OH)(O2CC6H4-p-OMe)(tmen)(2)(H2O)](ClO4)(2) (2) (tmen = N,N,N',N'-tetramethylethane-1,2-diamine), were prepared and structurally characterized. Complex 1 crystallizes in the monoclinic space group P2(1)/a with a = 17.718(2), b = 9.869(1), c = 19.677(2) Angstrom, beta = 115.16(1)degrees, V = 3114.3(6) Angstrom(3) and Z = 4. The structure was refined to R(wR(2)) = 0.067(0.178). Complex 2 crystallizes in the monoclinic space group P2(1)/a with a = 17.695(3), b = 9.574(4), c = 20.104(2) Angstrom, beta = 114.18(1)degrees, V = 3107(1) Angstrom(3) and Z = 4. The final residuals are R(wR(2)) = 0.067(0.182). The complexes have a [Cu-2(mu-OH)(mu-OH)(mu-O2CAr)](2+) core with tmen Ligands occupying the terminal sites of the core. In addition, one copper is axially bound to a water molecule. The Cu ... Cu distances and the Cu-OH Cu angles in the core are 3.394(1) Angstrom, 124.4(2)degrees for 1 and 3.374(1) Angstrom, 123.3(3)degrees for 2. The complexes show axial X-band EPR spectral features in methanol glass at 77 K giving g(perpendicular to) = 2.02, g(parallel to) = 2.3 (A(parallel to) = 165 x 10(-4) cm(-1)) and a visible band near similar to 630 nm in methanol. The complexes are weakly antiferromagnetic. A theoretical fit of the magnetic susceptibility data in the temperature range 40-295 K gives -J = 10 cm(-1), g = 2.05 for 1 and -J = 10 cm(-1), g = 2.0 for 2. Plots of -2J versus the Cu-OH-Cu angle (phi) in this class of asymmetrically dibridged dicopper(II) complexes having d(x2-y2)-d(x2-y2) magnetic orbitals show a linear magneto-structural correlation: -2J(cm(-1)) = 11.48 phi(deg) - 1373.

Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes

The coordinating behavior of a new dihydrazone ligand, 2,6-bis(3-methoxysalicylidene) hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with alpha=98.491(10)degrees, beta=110.820(10)degrees and gamma=92.228(10)degrees. The cell dimensions are a=10.196(7)angstrom, b=10.814(7)angstrom, c=10.017(7)angstrom, Z=2 and V=1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with g(iso) = 2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible. (C) 2011 Elsevier B.V. All rights reserved.

New lithium-ion conductors based on the NASICON structure

Lithium-ion conduction in mixed-metal phosphates, (LiMMIII)-M-V(PO,), [M-V = Nb, Ta; M-III = Al, Cr, Fe], possessing the rhombohedral (R (3) over bar c) NASICON structure has been investigated. Among the phosphates investigated, LiTaAl(PO4)(3) exhibits the highest conductivity, sigma approximate to 1.0 x 10(-2) S cm(-1) at 350 degrees C (E-a = 0.47 eV), comparable to the conductivity of LiTi2(PO4)(3). Unlike LiTi2(PO4)(3) which contains lithium-reducible Ti-IV, LiTaAl(PO4)(3) contains stable Ta-V and Al-III oxidation states and hence deserves further attention towards tailoring new lithium-ion conductors for application as electrolytes in solid state lithium batteries.

Synthesis, crystal structure and magnetic properties of a polymeric copper(II) Schiff-base complex having binuclear units covalently linked by isonicotinate ligands

The polynuclear copper(II) complex [{Cu2L(O2CC5H4N)}. C2H5OH](x) (1), where H3L is a 1∶2 Schiff base derived from 1,3-diaminopropan-2-ol and salicylaldehyde, has been prepared and structurally characterized. The structure consists of a one-dimensional zigzag chain in which the binuclear [Cu2L](+) units are covalently linked by isonicotinate ligands to give a syndiotactic arrangement of the copper ions protruding outside the chain. In the basic unit, the copper(II) centres are bridged by an alkoxo and a carboxylato ligand, giving a Cu ... Cu distance of 3.492(3) Angstrom and a Cu-O-Cu angle of 130.9(2)degrees. While one copper centre has a square-planar geometry, the other copper is square-pyramidal with the pyridine nitrogen being the axial ligand. The visible electronic spectrum of 1 shows a broad d-d band at 615 nm. The complex shows a rhombic X-band EPR spectral pattern in the polycrystalline phase at 77 K. Magnetic susceptibility measurements in the temperature range 22 to 295 K demonstrate the antiferromagnetic behaviour of 1. A theoretical fit to the magnetic data is based on a model assuming 1 as an equimolar mixture of copper atoms belonging to an antiferromagnetically coupled one-dimensional Heisenberg chain with the other copper atoms outside the chain behaving like paramagnetic centres.

Crystal structure and thermal and electrical properties of the perovskite solid solution Nd1-xSrxFeO3-delta (0 <= x <= 0.4)

The crystal structure, thermal expansion and electrical conductivity of strontium-doped neodymium ferrite (Nd1-xSrxFeO3-delta where 0less than or equal toxless than or equal to0.4) were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction. The orthorhombic distortion decreases with increasing Sr substitution. The pseudocubic lattice parameter shows a minimum at x=0.3. The thermal expansion curves for x=0.2-0.4 displayed rapid increase in slope at higher temperatures. The electrical conductivity increased with Sr content and temperature. The calculated activation energies for electrical conduction decreased with increasing x. The electrical conductivity can be described by the small polaron hopping mechanism. The charge compensation for divalent ion on the A-site is provided by the formation of Fe4+ ions on the B site and vacancies on the oxygen sublattice. The results indicate two defect domains: for low values of x, the predominant defect is Fe4+ ions, whereas for higher values of x, oxygen vacancies dominate. (C) 2002 Elsevier Science B.V. All rights reserved.

Crystal structure, thermal expansion and electrical conductivity of Nd0.7Sr0.3Fe1-xCoxO3 (0 <= x <= 0.8)

The crystal structure, thermal expansion and electrical conductivity of the solid solution Nd0.7Sr0.3Fe1-xCoxO3 for 0 less than or equal to x less than or equal to 0.8 were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction (XRPD). The pseudo-cubic lattice constant decreased continuously with x. The average linear thermal expansion coefficient (TEC) in the temperature range from 573 to 973 K was found to increase with x. The thermal expansion curves for all values of x displayed rapid increase in slope at high temperatures. The electrical conductivity increased with x for the entire temperature range of measurement. The calculated activation energy values indicate that electrical conduction takes place primarily by the small polaron hopping mechanism. The charge compensation for the divalent ion on the A-site is provided by the formation of Fe4+ ions on the B-site (in preference to Co4+ ions) and vacancies on the oxygen sublattice for low values of x. The large increase in the conductivity with x in the range from 0.6 to 0.8 is attributed to the substitution of Fe4+ ions by Co4+ ions. The Fe site has a lower small polaron site energy than Co and hence behaves like a carrier trap, thereby drastically reducing the conductivity. The non-linear behaviour in the dependence of log sigmaT with reciprocal temperature can be attributed to the generation of additional charge carriers with increasing temperature by the charge disproportionation of Co3+ ions. (C) 2002 Elsevier Science B.V. All rights reserved.