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.

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.

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.

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.

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

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.

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.