Spectroscopic and thermodynamic characterization of a cobalt-verdazyl valence tautomeric system. influence of crystal structure, solvent and counterion.

Crystallization of the verdazyl-based valence tautomeric ion [Co(dipyvd)] (where dipyvd is the radical ligand 1-isopropyl-3,5-di(2'-pyridyl)-6-oxoverdazyl) with a variety of different counterions results in materials that show varying degrees of valence tautomeric (VT) transition in the solid state. The X-ray structure of the SbF salt at 150 K reveals a localized structure for the = 1/2 tautomer, with a Co cation and distinct anionic and radical ligands. Comparison with the structure of the same material at 300 K reveals large structural changes in the ligand as a result of the valence tautomeric equilibrium.

Metal-ligand interactions in a redox active ligand system. Electrochemistry and spectroscopy of [M(dipyvd)] (M=Zn, Ni, =0, 1, 2).

Reaction of nickel and zinc triflates with the tridentate leucoverdazyl 1-isopropyl-3,5-di (2'-pyridyl)-6-oxo-2H-tetrazine (dipyvdH) and triethylamine resulted in the neutral coordination compounds M(dipyvd) (M = Ni,Zn). In acetonitrile, both compounds undergo two one electron oxidation processes, Zn (dipyvd) at -0.28 V and -0.

[1,2,4]triazolo[4,3-]quinoxaline as Novel Scaffold in the Imiqualines Family: Candidates with Cytotoxic Activities on Melanoma Cell Lines.

Cutaneous melanoma is one of the most aggressive human cancers and is the deadliest form of skin cancer, essentially due to metastases. Novel therapies are always required, since cutaneous melanoma develop resistance to oncogenic pathway inhibition treatment. The Imiqualine family is composed of heterocycles diversely substituted around imidazo[1,2-]quinoxaline, imidazo[1,2-]pyrazine, imidazo[1,5-]quinoxaline, and pyrazolo[1,5-]quinoxaline scaffolds, which display interesting activities on a panel of cancer cell lines, especially melanoma cell lines.

Elucidating the Role of the Metal Catalyst and Oxide Support in the Ru/CeO-Catalyzed CO Methanation Mechanism.

This study addresses the yet unresolved CO methanation mechanism on a Ru/CeO catalyst by means of near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) complemented with periodic density functional theory (DFT) calculations. NAP-XPS results show that the switch from H to CO + H mixture oxidizes both the Ru and CeO phases at low temperatures, which is explained by the CO adsorption modes assessed by means of DFT on each representative surface. CO adsorption on Ru is dissociative and moderately endergonic, leading to polybonded Ru-carbonyl groups whose hydrogenation is the rate-determining step in the overall process.

Thermocatalytic CO Conversion over a Nickel-Loaded Ceria Nanostructured Catalyst: A NAP-XPS Study.

Despite the increasing economic incentives and environmental advantages associated to their substitution, carbon-rich fossil fuels are expected to remain as the dominant worldwide source of energy through at least the next two decades and perhaps later. Therefore, both the control and reduction of CO emissions have become environmental issues of major concern and big challenges for the international scientific community. Among the proposed strategies to achieve these goals, conversion of CO by its reduction into high added value products, such as methane or syngas, has been widely agreed to be the most attractive from the environmental and economic points of view.

Heteroleptic Iron(II) Spin-Crossover Complexes Based on a 2,6-Bis(pyrazol-1-yl)pyridine-type Ligand Functionalized with a Carboxylic Acid.

Two new heteroleptic complexes [Fe(1bppCOOH)(3bpp-bph)](ClO)·solv (, solv = various solvents; 1bppCOOH = 2,6-bis(1-pyrazol-1-yl)isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1'-biphenyl]-4-yl)-1-pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)(1bppCOOEt)](ClO)·0.5MeCO (, 1bppCOOEt = ethyl 2,6-bis(1-pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound was obtained by the combination of stoichiometric amounts of Fe(ClO), 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH)](ClO).

Towards chemically neutral carbon cleaning processes: plasma cleaning of Ni, Rh and Al reflective optical coatings and thin Al filters for free-electron lasers and synchrotron beamline applications.

The choice of a reflective optical coating or filter material has to be adapted to the intended field of application. This is mainly determined by the required photon energy range or by the required reflection angle. Among various materials, nickel and rhodium are common materials used as reflective coatings for (soft) X-ray mirrors.

Magnetoresistance in Hybrid Pt/CoFeO Bilayers Controlled by Competing Spin Accumulation and Interfacial Chemical Reconstruction.

Pure spin currents have potential for use in energy-friendly spintronics. They can be generated by a flow of charge along a nonmagnetic metal with large spin-orbit coupling. This produces a spin accumulation at the surfaces, controllable by the magnetization of an adjacent ferromagnetic layer.

Characterization of Carbon-Contaminated BC-Coated Optics after Chemically Selective Cleaning with Low-Pressure RF Plasma.

Boron carbide (BC) is one of the few materials that is expected to be most resilient with respect to the extremely high brilliance of the photon beam generated by free electron lasers (FELs) and is thus of considerable interest for optical applications in this field. However, as in the case of many other optics operated at light source facilities, BC-coated optics are subject to ubiquitous carbon contaminations. Carbon contaminations represent a serious issue for the operation of FEL beamlines due to severe reduction of photon flux, beam coherence, creation of destructive interference, and scattering losses.

Emerging Diluted Ferromagnetism in High- Superconductors Driven by Point Defect Clusters.

Defects in ceramic materials are generally seen as detrimental to their functionality and applicability. Yet, in some complex oxides, defects present an opportunity to enhance some of their properties or even lead to the discovery of exciting physics, particularly in the presence of strong correlations. A paradigmatic case is the high-temperature superconductor YBaCuO (Y123), in which nanoscale defects play an important role as they can immobilize quantized magnetic flux vortices.

Design and performance of BOREAS, the beamline for resonant X-ray absorption and scattering experiments at the ALBA synchrotron light source.

The optical design of the BOREAS beamline operating at the ALBA synchrotron radiation facility is described. BOREAS is dedicated to resonant X-ray absorption and scattering experiments using soft X-rays, in an unusually extended photon energy range from 80 to above 4000 eV, and with full polarization control. Its optical scheme includes a fixed-included-angle, variable-line-spacing grating monochromator and a pair of refocusing mirrors, equipped with benders, in a Kirkpatrick-Baez arrangement.

High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite PbFeOsO.

PbFeOsO was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe-Os antisite occupancy of about 16.

Custom sample environments at the ALBA XPEEM.

A variety of custom-built sample holders offer users a wide range of non-standard measurements at the ALBA synchrotron PhotoEmission Electron Microscope (PEEM) experimental station. Some of the salient features are: an ultrahigh vacuum (UHV) suitcase compatible with many offline deposition and characterization systems, built-in electromagnets for uni- or biaxial in-plane (IP) and out-of-plane (OOP) fields, as well as the combination of magnetic fields with electric fields or current injection. Electronics providing a synchronized sinusoidal signal for sample excitation enable time-resolved measurements at the 500MHz storage ring RF frequency.

The ALBA spectroscopic LEEM-PEEM experimental station: layout and performance.

The spectroscopic LEEM-PEEM experimental station at the CIRCE helical undulator beamline, which started user operation at the ALBA Synchrotron Light Facility in 2012, is presented. This station, based on an Elmitec LEEM III microscope with electron imaging energy analyzer, permits surfaces to be imaged with chemical, structural and magnetic sensitivity down to a lateral spatial resolution better than 20 nm with X-ray excited photoelectrons and 10 nm in LEEM and UV-PEEM modes. Rotation around the surface normal and application of electric and (weak) magnetic fields are possible in the microscope chamber.

k=0 magnetic structure and absence of ferroelectricity in SmFeO3.

SmFeO3 has attracted considerable attention very recently due to its reported multiferroic properties above room temperature. We have performed powder and single crystal neutron diffraction as well as complementary polarization dependent soft X-ray absorption spectroscopy measurements on floating-zone grown SmFeO3 single crystals in order to determine its magnetic structure. We found a k=0 G-type collinear antiferromagnetic structure that is not compatible with inverse Dzyaloshinskii-Moriya interaction driven ferroelectricity.

Two-dimensional electron gases at LaAlO3/SrTiO3 interfaces: orbital symmetry and hierarchy engineered by crystal orientation.

Recent findings show the emergence of two-dimensional electron gases (2DEGs) at LaAlO(3)/SrTiO(3) interfaces along different orientations; yet details on band reconstructions have remained so far unknown. Via x-ray linear dichroism spectroscopy, we demonstrate that crystal symmetry imposes distinctive 2DEG orbital hierarchies on (001)-and (110)-oriented quantum wells, allowing selective occupancy of states of different symmetry. Such orientational tuning expands the possibilities for electronic engineering of 2DEGs and opens up enticing opportunities to understand the link between orbital symmetry and complex correlated states at LaAlO(3)/SrTiO(3) quantum wells.

Characterization, optimization and surface physics aspects of in situ plasma mirror cleaning.

Although the graphitic carbon contamination of synchrotron beamline optics has been an obvious problem for several decades, the basic mechanisms underlying the contamination process as well as the cleaning/remediation strategies are not understood and the corresponding cleaning procedures are still under development. In this study an analysis of remediation strategies all based on in situ low-pressure RF plasma cleaning approaches is reported, including a quantitative determination of the optimum process parameters and their influence on the chemistry as well as the morphology of optical test surfaces. It appears that optimum results are obtained for a specific pressure range as well as for specific combinations of the plasma feedstock gases, the latter depending on the chemical aspects of the optical surfaces to be cleaned.

Direct observation of rotatable uncompensated spins in the exchange bias system Co/CoO-MgO.

We have observed a large exchange bias field HE ≈ 2460 Oe and a large coercive field HC ≈ 6200 Oe at T = 2 K for Co/CoO core-shell nanoparticles (~4 nm diameter Co metal core and CoO shell with ~1 nm thickness) embedded in a non-magnetic MgO matrix. Our results are in sharp contrast to the small exchange bias and coercive field in the case of a non-magnetic Al2O3 or C matrix materials reported in previous studies. Using soft X-ray magnetic circular dichroism at the Co-L2,3 edge, we have observed a ferromagnetic signal originating from the antiferromagnetic CoO shell.

Surface symmetry-breaking and strain effects on orbital occupancy in transition metal perovskite epitaxial films.

The electron occupancy of 3d-orbitals determines the properties of transition metal oxides. This can be achieved, for example, through thin-film heterostructure engineering of ABO(3) oxides, enabling emerging properties at interfaces. Interestingly, epitaxial strain may break the degeneracy of 3d-e(g) and t(2g) orbitals, thus favoring a particular orbital filling with consequences for functional properties.

Buried interfacial layer of highly oriented molecules in copper phthalocyanine thin films on polycrystalline gold.

The growth of copper phthalocyanine thin films evaporated on polycrystalline gold is examined in detail using near edge x-ray absorption fine structure spectroscopy and surface sensitive x-ray photoemission spectroscopy. The combination of both methods allows distinguishing between the uppermost layers and buried interface layers in films up to approximately 3 nm thickness. An interfacial layer of approximately 3 ML of molecules with an orientation parallel to the substrate surface was found, whereas the subsequent molecules are perpendicular to the metal surface.