(Cu)tet(Cr2-xSnx)octS4-ySey Spinels: Crystal Structure, Density Functional Theory Calculations, and Magnetic Behavior.

A new series of (Cu)tet[Cr2-xSnx]octS4-ySey compounds was prepared by solid-state reaction at high temperature. Determination of the crystal structures by single-crystal X-ray diffraction revealed that CuCr1.0Sn1.0S2.1Se1.9, CuCr1.2Sn0.8S2.1Se1.9, CuCr1.3Sn0.7S2.2Se1.8, and CuCr1.5Sn0.5S2.2Se1.8 crystallize in a normal spinel-type structure (cubic Fd3m space group). The powder X-ray diffraction patterns and Rietveld refinements of nominal CuCr2-xSnxS2Se2 (x = 0.2, 0.4, 0.6, 0.8, and 1.0) were consistent with single-crystal X-ray diffraction data. Raman scattering analysis revealed that the A1g, Eg, and three F2g vibrational modes were observed in the spectra. The signal at ∼382 cm-1, corresponding to the A1g mode, is attributed to symmetrical stretching of the chalcogen bond with respect to the tetrahedral metal. The samples with x = 0.2 and 0.4 exhibited ferromagnetic behavior, characterized by large positive θ values of +261 and +189 K, respectively. In contrast, antiferromagnetic (AF) behavior was observed for CuCrSnS2Se2 with a Néel temperature (TN) of 18.8 K and a θ value of -36.0 K. Density functional theory (DFT) and effective magnetic moments (µeff/µtheo) experimentally measured showed that the Sn ion is in oxidation state of 4+, i.e., diamagnetic behavior. DFT calculations revealed that the most stable magnetic state of CuCr1.0Sn1.0S2Se2 was AF with exchange constants for first- and second-neighbor interactions of J1 = 56.22 cm-1 and J2 = -33.88 cm-1. Thus, the AF interactions between ferromagnetic chains in CuCr1.0Sn1.0S2Se2 originate from the presence of diamagnetic Sn cations.

Magnetic properties of weakly exchange-coupled high spin Co(II) ions in pseudooctahedral coordination evaluated by single crystal X-band EPR spectroscopy and magnetic measurements.

We report single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(µ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S'= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (|JAB(1/2)| = 0.055(2) cm(­1)) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (|JAA(1/2)| ≈ 0.25 (1) cm(­1)), in good agreement with the average J(3/2) value determined from magnetic measurements.

Structural Characterization and Magnetic Behavior Due to the Cationic Substitution of Lanthanides on Ferrite Nanoparticles.

A new series of [Fe3-xLnx]O4 nanoparticles, with Ln = Gd; Dy; Lu and x = 0.05; 0.1; 0.15, was synthesized using the coprecipitation method. Analyses by X-ray diffraction (XRD), Rietveld refinement, and high-resolution transmission electron microscopy (HRTEM) indicate that all phases crystallized in space group Fd3¯m, characteristic of spinels. The XRD patterns, HRTEM, scanning electron microscopy analysis (SEM-EDS), and Raman spectra showed single phases. Transmission electron microscopy (TEM), Rietveld analysis, and Scherrer's calculations confirm that these materials are nanoparticles with sizes in the range of ~6 nm to ~13 nm. Magnetic measurements reveal that the saturation magnetization (Ms) of the as-prepared ferrites increases with lanthanide chemical substitution (x), while the coercivity (Hc) has low values. The Raman analysis confirms that the compounds are ferrites and the Ms behavior can be explained by the relationship between the areas of the signals. The magnetic measurements indicate superparamagnetic behavior. The blocking temperatures (TB) were estimated from ZFC-FC measurements, and the use of the Néel equation enabled the magnetic anisotropy to be estimated.

Study of nanocrystalline BiMnO3-PbTiO3: synthesis, structural elucidation, and magnetic characterization of the whole solid solution.

In the last ten years, the study and the search for new multiferroic materials have been a major challenge due to their potential applications in electronic technology. In this way, bismuth-containing perovskites (BiMO(3)), and particularly those in which the metal M position is occupied by a magnetically active cation, have been extensively investigated as possible multiferroic materials. From the point of view of synthesis, only a few of the possible bismuth-containing perovskites can be prepared by conventional methods but at high pressures. Herein, the preparation of one of these potential multiferroic systems, the solid solution xBiMnO(3)-(1-x)PbTiO(3) by mechanosynthesis is reported. Note that this synthetic method allows the oxides with high x values, and more particularly the BiMnO(3) phase, to be obtained as nanocrystalline phases, in a single step and at room temperature without the application of external pressure. These results confirm that, in the case of Bi perovskites, mechanosynthesis is a good alternative to high-pressure synthesis. These materials have been studied from the point of view of their structural characteristics by precession electron diffraction and magnetic property measurements.

Magnetism and structure in chains of copper dinuclear paddlewheel units.

An anhydrous copper carboxylate compound of formula [Cu(trans-2-butenoate)(2)](n) has been characterized. X-ray analysis reveals a structure built by paddlewheel units bridged by pairs of Cu...O axial bonds to give infinite chains arranged in a new topological motif. Susceptibility measurements in the 10-300 K temperature range, and isothermal magnetization curves at 2, 5, 10, and 50 K with fields up to 5 T, were obtained. Electron Paramagnetic Resonance (EPR) spectra of powder samples were measured at 33.9 GHz at 300 K, and at 9.60 GHz at temperatures in the range 90

Pyrophosphate-bridged Cu(II) chain magnet: {[Na3Cu(P2O7)(NO3)].3H2O}n.

A Cu(II)...Cu(II) pyrophosphate-bridged compound of formula {[Na(3)Cu(P(2)O(7))(NO(3))].3H(2)O}(n) (1) has been characterized. X-ray diffraction measurements show that it crystallizes in the monoclinic space group P2(1)/m, with unit cell dimensions a = 7.2492(5) A, b = 8.2446(6) A, c = 9.9050(7) A, beta = 107.123(1) degrees, and Z = 2. The structure consists of chains of Cu(II) cations at inversion symmetry sites bound to four equatorial oxygen atoms provided by two pyrophosphate anions halved by a symmetry plane and two axial oxygen atoms of nitrate anions. The molar magnetic susceptibility chi(0) of a powdered sample was measured in the temperature range 2 K < T < 273 K, and an isothermal magnetization curve, M(B(0),T), was obtained at T = 30 K, with the magnetic field B(0) between 0 and 5 T. Fitting a spin-chain model to the susceptibility data, we evaluate an antiferromagnetic exchange coupling 2J = -24.3(1) cm(-1) (defined as H(ex) = -2JS(i)S(j)) between Cu(II) neighbors. For any orientation of B(0), single-crystal electron paramagnetic resonance (EPR) spectra obtained at 9.8 and 33.9 GHz at 300 K display a single signal having a g matrix with orthorhombic symmetry, arising from the merger produced by the exchange interaction of the resonances corresponding to the two rotated Cu(II) sites. The g matrices of the individual molecules calculated assuming axial symmetry yielded principal values g(parallel) = 2.367(1) and g(perpendicular) = 2.074(1) at both frequencies, indicating a d(x(2)-y(2)) ground-state orbital for the Cu(II) ions. The angular variation of the EPR line width suggests exchange narrowing in a system with one-dimensional spin dynamics, as expected from the structure and susceptibility data. The results, discussed in terms of the crystal and electronic structures and of the spin dynamics of the compound, are compared with those obtained in other materials.

Ni/Ni oxides nanoparticles with potential biomedical applications obtained by displacement of a nickel-organometallic complex.

A new synthesis and stabilization method was developed for paramagnetic nanoparticles composed of nickel and nickel oxides. Nickel/nickel oxides nanoparticles were synthesized by a method based on ligand displacement of bis(1,5-cyclooctadiene)-nickel(0), zerovalent organometallic precursor and simultaneous formation of a thiourea inclusion compound. Nickel/nickel oxides nanoparticles were stabilized with the amphipathic peptide H2N-Cys-Leu-Pro-Phe-Phe-Asp-NH2 having H2N-Leu-Pro-Phe-Phe-Asp-NH2 a peptide with potential properties for Alzheimer's disease therapy. The inclusion compound formed after displacement was characterized by X-ray powder diffraction, and nickel/nickel oxides nanoparticles were characterized using transmission electron microscopy, atomic force microscopy, UV-Visible spectroscopy, X-ray photoelectron spectroscopy, and superconducting quantum interference device magnetometry. In addition, a cell viability assay in primary rat hippocampal neurons was carried out.

Synthesis, crystal structure and magnetic properties of diaquabis(2,6-diamino-7H-purin-1-ium-κN9)bis(4,4'-oxydibenzoato-κO)cobalt(II) dihydrate.

The title mononuclear CoII complex, [Co(C5H7N6)2(C14H8O5)2(H2O)2]·2H2O, has been synthesized and its crystal structure determined by X-ray diffraction. The complex crystallizes in the triclinic space group P-1, with one formula unit per cell (Z = 1 and Z' = 1/2). It consists of a mononuclear unit with the CoII ion on an inversion centre coordinated by two 2,6-diamino-7H-purin-1-ium cations, two 4,4'-oxydibenzoate anions (in a nonbridging κO-monodentate coordination mode, which is less common for the anion in its CoII complexes) and two water molecules, defining an octahedral environment around the metal atom. There is a rich assortment of nonbonding interactions, among which a strong N+-H...O- bridge, with a short N...O distance of 2.5272 (18) Å, stands out, with the H atom ostensibly displaced away from its expected position at the donor side, towards the acceptor. The complex molecules assemble into a three-dimensional hydrogen-bonded network. A variable-temperature magnetic study between 2 and 300 K reveals an orbital contribution to the magnetic moment and a weak antiferromagnetic interaction between CoII centres as the temperature decreases. The model leads to the following values: A (crystal field strength) = 1.81, λ (spin-orbit coupling) = -59.9 cm-1, g (Landé factor) = 2.58 and zJ (exchange coupling) = -0.5 cm-1.

A novel perovskite oxide chemically designed to show multiferroic phase boundary with room-temperature magnetoelectricity.

There is a growing activity in the search of novel single-phase multiferroics that could finally provide distinctive magnetoelectric responses at room temperature, for they would enable a range of potentially disruptive technologies, making use of the ability of controlling polarization with a magnetic field or magnetism with an electric one (for example, voltage-tunable spintronic devices, uncooled magnetic sensors and the long-searched magnetoelectric memory). A very promising novel material concept could be to make use of phase-change phenomena at structural instabilities of a multiferroic state. Indeed, large phase-change magnetoelectric response has been anticipated by a first-principles investigation of the perovskite BiFeO3-BiCoO3 solid solution, specifically at its morphotropic phase boundary between multiferroic polymorphs of rhombohedral and tetragonal symmetries. Here, we report a novel perovskite oxide that belongs to the BiFeO3-BiMnO3-PbTiO3 ternary system, chemically designed to present such multiferroic phase boundary with enhanced ferroelectricity and canted ferromagnetism, which shows distinctive room-temperature magnetoelectric responses.

Magnetic Interactions in the Copper Complex (L-Aspartato)(1,10-phenanthroline)copper(II) Hydrate. An Exchange-Coupled Extended System with Two Dissimilar Copper Ions.

We report EPR measurements in single-crystal samples at the microwave frequencies 9.8 and 34.3 GHz and magnetic susceptibility measurements in polycrystalline samples for the ternary complex of copper with aspartic acid and phenanthroline, (L-aspartato)(1,10-phenanthroline)copper(II) hydrate. The crystal lattice of this compound is composed of two dissimilar copper ions identified as Cu(A) and Cu(B), which are in two types of copper chains called A and B, respectively, running parallel to the b crystal axis. The copper ions in the A chains are connected by the aspartic acid molecule, and those in the B chains by a chemical path that involves a carboxylate bridge and a hydrogen bond. Both chains are held together by a complex network of hydrogen bonds and by hydrophobic interactions between aromatic amines. Magnetic susceptibility data indicate a Curie-Weiss behavior in the studied temperature range (2-300 K). The EPR spectra at 9.8 GHz display a single exchange collapsed resonance for any magnetic field orientation, in the so-called strong exchange regime. Those at 34.3 GHz are within the so-called weak exchange regime and display two resonances which belong to each type of copper ion chain. The decoupling of the spectra at 34.3 GHz using a theory based on Anderson's model for the case of two weakly exchange coupled spins S = (1)/(2) allows one to obtain the angular variation of the squares of the g-factor and the peak-to-peak line width of each resonance. This model also allows one to evaluate the exchange parameter |J(AB)/k| = 2.7(6) mK associated with the chemical path connecting dissimilar copper ions. The line width data obtained for each component of the spectra at 34.3 GHz are analyzed in terms of a model based on Kubo and Tomita's theory, to obtain the exchange parameters |J(A)/k| = 0.77(2) K and |J(B)/k| = 1.44(2) K associated with the chemical paths connecting the similar copper ions of types A and B, respectively.

Two polymorphic forms of a mixed zinc/copper biquinoline dihydrogenphosphate.

Two polymorphic forms of a mixed zinc/copper biquinoline dihydrogenphosphate are presented, showing almost identical monomeric units, viz. (2,2'-biquinoline-kappa(2)N,N')bis(dihydrogenphosphato-kappaO)copper(II)/zinc(II), formulated as [Zn(x)Cu(1-x)(H(2)PO(4))(2)(C(18)H(12)N(2))], with x = 0.88 (1) and 0.90 (2). The cation is tetrahedrally coordinated to a chelating biquinoline system and two diprotonated phosphate anions. The structures differ mainly in their intermolecular hydrogen-bonding interactions, leading to different packing schemes. No significant evidence of stress due to the Zn/Cu solid solution formation was detected.

New anionic cobalt complexes using highly hindered bis-amides with varying donor abilities as ligands.

Four potential tetradentate ligands of formulae 1,2-bis-(3,5-di-tert-butyl-2-hydroxybenzamido)ethane (H(4)L(1), 1), 1,2-bis-(3,5-di-tert-butyl-2-hydroxybenzamido)propane (H(4)L(2), 2), 1,2-bis-(3,5-di-tert-butyl-2-hydroxybenzamido)benzene (H(4)L(3), 3) and 1,8-bis-(3,5-di-tert-butyl-2-hydroxybenzamido)naphthalene (H(4)L(4), 4) have been prepared and the crystal structures of three of them (1, 3 and 4) determined by single crystal X-ray diffraction. The investigation of their complexing ability toward Co(II) afforded the compounds of formulae [Co(III)(L(3))Na(I)(H(2)O)(2)] (5), [Co(III)(L(n))Li(I)(H(2)O)2] with n = 1 (6), 2 (7) and 3 (8) and [Co(II)(L(4))Li(I)(2)] (9). Complexes 5-8 are square planar Co(III) species, as corroborated by the crystal structure of 5. In this compound, two amide-nitrogen and two phenolate-oxygen atoms of a fully deprotonated (L(3))(4-) anion build a slightly distorted square planar surrounding around the cobalt atom, the Co-N distances [1.858(3) and 1.861(3) A] being somewhat longer than the Co-O ones [1.798(3) and 1.801(3) A]. Magnetic and 1H NMR data at room temperature for 6-8 support the occurrence of an intermediate S = 1 low-lying state for the Co(III) center which is stabilized by the strong donating ability of the fully deprotonated bis-amidate ligands. In the case of the compound with the naphthalene derivative (9), the analytical and spectroscopic data suggest the occurrence of a low spin Co(II) complex. The weakening of the ligand field strength of the tetradentate bis-amidate ligand in the naphthalene derivative (5-6-5 ring-membered fused chelate) when compared to the situation in complexes 5-8 (5-5-5 ring-membered fused chelate) would account for this feature.

An unusual eight-coordinated copper complex: bis(4,7-diphenyl-1,10-phenanthroline)dinitratocopper(II).

In the title monomer, [Cu(NO3)2(C24H16N2)2], the copper(II) cation is eight-coordinate within an octahedral-like polyhedron. The coordination polyhedron is formed by two chelating diphenylphenanthroline groups that define the highly distorted CuN4 equatorial plane and two weakly bound bidentate (chelating) nitrate groups in the apical or axial positions. The complex crystallizes in the monoclinic space group C2/c; a twofold axis passes through the copper(II) cation and bisects the two nitrate ligands. This gives the molecule C2 point-group symmetry, rendering only half of the molecule independent.

Gadolinium and neodymium citrates: evidence for weak ferromagnetic exchange between gadolinium(III) cations.

A new lanthanide citrate motif of general formula [Ln(Hcit)(H2O)2.H2O]n, where Ln = Gd (1) and Nd (2) and Hcit3- = C(OH)(COO-)(CH2COO-)2, has been synthesized hydrothermally from Ln2O3 and citric acid at 100 degrees C and characterized by elemental analysis, IR, TG-DTA, single-crystal X-ray diffraction, and magnetic measurements. The structures can be seen as "ladder chains" along the a axis, with dinuclear Ln2O2 units serving as "steps" and R-COO groups as "uprights", which are connected by H bonds. The magnetic susceptibility between 2 and 300 K and the magnetization at 2 K, as a function of magnetic field between 0 and 5 T, were measured for both compounds. By modeling the magnetic behavior of the Gd compound with a dinuclear Hamiltonian [symbol: see text](S) = gmu(B)(S(A) + S(B))B(o) - J(o)S(A)S(B) (S(A) = S(B) = 7/2), a ferromagnetic exchange interaction J(o) = 0.039 cm(-1) was evaluated between Gd ions situated at d(o) = 4.321 angstroms in dinuclear units bridged by two symmetry-related tridentate carboxylate oxygens. The EPR spectrum of the Gd compound is discussed. The temperature dependence of the susceptibility of the Nd compound is caused by the depopulation of the excited crystal-field levels when the temperature decreases. The magnetic-field dependence of the magnetization of 2 is attributed to the ground-state Kramers' doublet populated at 2 K. The g factor of this ground-state doublet is calculated from the data and compared with values for other compounds reported in the literature.

Carboxylate-bridged copper(II)-lanthanide(III) complexes [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n)(Ln = Dy, Ho, Er, Y; oda = oxydiacetate).

The hydrothermal reaction of Ln(2)O(3) (Ln = Dy and Ho), Cu(OAc)(2).2H(2)O, and oxydiacetic acid in the approximate mole ratio of 1:3:8 resulted in the formation of two new members of the isostructural series of polymers formulated as [(Cu(3)Ln(2)(oda)(6)(H(2)O)(6)).12H(2)O](n), crystallizing in the hexagonal crystal system, space group P6/mcc (No. 192). Temperature-dependent magnetic susceptibilities and EPR spectra are reported for the heterometallic compounds Cu-Dy 1, Cu-Ho 2, Cu-Er 3, and Cu-Y 4. The results are discussed in terms of the structure of the compounds, the electronic properties of the lanthanide ions, and the exchange interactions between the magnetic ions.