Physical properties of new ordered bimetallic phases M0.25Cd0.75PS3 (M = ZnII, NiII, CoII, MnII).

Four bimetallic phases of the thiophosphate family have been synthesized by the cationic exchange reaction using a freshly prepared K0.5Cd0.75PS3 precursor phase and methanolic solutions of nitrates of the divalent cations ZnII, NiII, CoII, and MnII. All the materials were characterized by FTIR, PXRD, SEM-EDXS and (in the case of the diamagnetic compounds) by solid state NMR. For the K0.5Cd0.75PS3 precursor, the X-ray powder diffraction data suggest a modification of the structure, while solid state NMR results confirm that this phase possesses an ordered arrangement of Cd vacancies. The cationic exchange reaction achieves a complete removal of potassium ions (no potassium detected by SEM-EDXS) and re-occupation of the vacancies by divalent cations. Therefore, the obtained compounds have an average composition of M0.25Cd0.75PS3 (M = ZnII, NiII, CoII, MnII) and possess an ordered distribution of the substituent cations. Even with the paramagnetic substitution level of 25%, antiferromagnetic behaviour is present in the phases with MnII, CoII and NiII, as evidenced by dc susceptibility and in the case of the MnII substituted phase by EPR. The cooperative magnetic interactions confirm the conclusion that the paramagnetic ions adopt an ordered arrangement. The analysis by broad band impedance spectroscopy allows to attribute the conductivity in these materials to charge movements in the layers due to the difference in electronegativity of the metal ions. Zn0.25Cd0.75PS3 is the phase that shows the highest conductivity values. Finally, the band gap energies of the bimetallic phases tend to be lower than those of the single-metal phases, probably due to an overlap of the band structures.

Magnetic behaviour of bimetallic layered phases M'0.2Mn0.8PS3·0.25 H2O (M' = ZnII, CuII, NiII, CoII).

In this work the magnetic properties of bimetallic phases M'0.2Mn0.8PS3·0.25H2O (M' = CoII, NiII, CuII or ZnII) have been explored and compared with those of the pristine phase MnPS3. Magnetic susceptibility, high field magnetization and electron paramagnetic resonance (EPR) studies reveal that the transition temperature between the antiferromagnetic and paramagnetic order for the pristine phase is shifted to lower values in the bimetallic phases. From magnetization measurements the critical field of the spin-flop transition is found to be dependent on the nature of the added secondary transition metal ion. EPR spectra of all compounds in the temperature range of 8-300 K present a single resonance line shape. Temperature dependence of the EPR parameters, like line width, g values and double integrated area (IDIN), are obtained from the spectra and present a scenario compatible with the magnetization results. The temperature dependence of the first derivative of the product (IDINT) shows two maxima for all samples, with exception of the CoII phase, indicating two critical temperatures, while these critical temperatures could not be clearly determined by dc susceptibility.

Light-Induced Structural Change in Iridium Complexes Studied by Electron Spin Resonance.

Iridium-based compounds are materials of great interest in the production of highly efficient organic light emitting diodes and several other applications. However, these organometallic compounds present relative low stability due to photodegradation processes still not well understood. In this work we investigated paramagnetic states induced by UV photoexcitation on iridium(III) bis[(4,6-fluorophenyl)-pyridinato-N,C2']picolinate (FIrpic) and iridium(III)-tris(2-phenylpyridine) (Ir(ppy)3) complexes dispersed in different polymeric matrices by electron spin resonance (ESR). Photogenerated charged states with relatively strong hyperfine interactions were observed and attributed to matrix/complex charge-transfer processes. Measurements of the signal amplitude decay after photoexcitation interruption were performed as a function of temperature. The photoinduced centers are thermally activated with energy barrier between 0.3 and 0.6 eV. Electronic structure calculations suggest that the signals observed by ESR are associated with metastable negatively charged Ir complexes distorted structures.

Luminescent DNA- and agar-based membranes.

Luminescent materials containing europium ions are investigated for different optical applications. They can be obtained using bio-macromolecules, which are promising alternatives to synthetic polymers based on the decreasing oil resources. This paper describes studies of the DNA- and Agar-europium triflate luminescent membranes and its potential technological applications are expanded to electroluminescent devices. Polarized optical microscopy demonstrated that the samples are birefringent with submicrometer anisotropy. The X-ray diffraction analysis revealed predominantly amorphous nature of the samples and the atomic force microscopy images showed a roughness of the membranes of 409.0 and 136.1 nm for the samples of DNA10Eu and Agar1.11Eu, respectively. The electron paramagnetic resonance spectra of the DNA(n)Eu membranes with the principal lines at g ≈ 2.0 and g ≈ 4.8 confirmed uniform distribution of rare earth ions in a disordered matrix. Moreover, these strong and narrow resonance lines for the samples of DNA(n)Eu when compared to the Agar(n)Eu suggested a presence of paramagnetic radicals arising from the DNA matrix. The emission spectra suggested that the Eu3+ ions occupy a single local environment in both matrices and the excitation spectra monitored around the Eu emission lines pointed out that the Eu3+ ions in the Agar host were mainly excited via the broad band component rather than by direct intra-4f(6) excitation, whereas the opposite case occurred for the DNA-based sample.

Deconvolution of the EPR spectra of vanadium oxide nanotubes.

In this work we report results of continuous wave (CW) electron paramagnetic resonance (EPR) spectroscopy of vanadium oxide nanotubes. The observed EPR spectra are composed of a weak well-resolved spectrum of isolated V(4+) ions on top of an intense and broad structure-less line shape, attributed to spin-spin exchanged V(4+) clusters. With the purpose to deconvolute the structured weak spectrum from the composed broad line, a new approach based on the Krylov basis diagonalization method (KBDM) is introduced. It is based on the discrimination between broad and sharp components with respect to a selectable threshold and can be executed with few adjustable parameters, without the need of a priori information on the shape and structure of the lines. This makes the method advantageous with respect to other procedures and suitable for fast and routine spectral analysis, which, in conjunction with simulation techniques based on the spin Hamiltonian parameters, can provide a full characterization of the EPR spectrum. Results demonstrate and characterize the coexistence of two V(4+) species in the nanotubes and show good progress toward the goal of obtaining high fidelity deconvoluted spectra from complex signals with overlapping broader line shapes.

Glass structure and ion dynamics of lead-cadmium fluorgermanate glasses.

Glass structure and fluorine motion dynamics are investigated in lead-cadmium fluorgermanate glasses by means of differential scanning calorimetry, Raman scattering, x-ray absorption (EXAFS), electrical conductivity (EC), and (19)F nuclear magnetic resonance (NMR) techniques. Glasses with composition 60PbGeO(3)-xPbF(2)-yCdF(2) (in mol %), with x+y=40 and x=10, 20, 30, 40, are studied. Addition of metal fluorides to the base PbGeO(3) glass leads to a decrease of the glass transition temperature (T(g)) and to an enhancement of the ionic conductivity properties. Raman and EXAFS data analysis suggest that metagermanate chains form the basic structural feature of these glasses. The NMR study leads to the conclusion that the F-F distances are similar to those found in pure crystalline phases. Experimental results suggest the existence of a heterogeneous glass structure at the molecular scale, which can be described by fluorine rich regions permeating the metagermanate chains. The temperature dependence of the NMR line shapes and relaxation times exhibits the qualitative and quantitative features associated with the high fluorine mobility in these systems.

Electron spin-relaxation via vibronic level of nickel (I) and nickel (III) cyanide complexes in NaCl single crystals.

Electron spin-lattice relaxation rates for the low spin [Ni(CN)(4)](1-) and [Ni(CN)(4)](3-) complexes in NaCl host lattice were measured by the inversion recovery technique in the temperature range 7-50K. The data for both paramagnetic species fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g-tensor temperature dependence.