Study of the Counter Cation Effects on the Supramolecular Structure and Electronic Properties of a Dianionic Oxamate-Based {NiII2} Helicate.

Herein, we describe the synthesis, crystal structure, and electronic properties of {[K2(dmso)(H2O)5][Ni2(H2mpba)3]·dmso·2H2O}n (1) and [Ni(H2O)6][Ni2(H2mpba)3]·3CH3OH·4H2O (2) [dmso = dimethyl sulfoxide; CH3OH = methanol; and H4mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni2(H2mpba)3]2- helicate, hereafter referred to as {NiII2}. SHAPE software calculations indicate that the coordination geometry of all the NiII atoms in 1 and 2 is a distorted octahedron (Oh) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D2d) and distorted octahedron (Oh), respectively. The {NiII2} helicate in 1 is connected by K+ counter cations yielding a 2D coordination network with sql topology. In contrast to 1, the electroneutrality of the triple-stranded [Ni2(H2mpba)3] 2- dinuclear motif in 2 is achieved by a [Ni(H2O)6]2+ complex cation, where the three neighboring {NiII2} units interact in a supramolecular fashion through four R22(10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the NiII/NiI pair being mediated by OH- ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The NiII ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K+ counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations.

Direct and Indirect Determination of the Magnetocaloric Effect in the Heusler Compound Ni1.7Pt0.3MnGa.

Magnetic shape-memory materials are potential magnetic refrigerants, due the caloric properties of their magnetic-field-induced martensitic transformation. The first-order nature of the martensitic transition may be the origin of hysteresis effects that can hinder practical applications. Moreover, the presence of latent heat in these transitions requires direct methods to measure the entropy and to correctly analyze the magnetocaloric effect. Here, we investigated the magnetocaloric effect in the Heusler material Ni1.7Pt0.3MnGa by combining an indirect approach to determine the entropy change from isofield magnetization curves and direct heat-flow measurements using a Peltier calorimeter. Our results demonstrate that the magnetic entropy change ΔS in the vicinity of the first-order martensitic phase transition depends on the measuring method and is directly connected with the temperature and field history of the experimental processes.

A versatile X-ray phase retarder for lock-in XMCD measurements.

X-ray magnetic circular dichroism (XMCD) is a technique commonly used to probe magnetic properties of materials with element and orbital selectivity, which requires the use of circularly polarized (CP) X-rays. It is possible to accomplish XMCD experiments with fixed CP and alternating the magnetic field orientation, but most reliable data are obtained when alternating the magnetization orientation and the polarization between right and left helicities. A versatile strategy has been developed to perform XMCD experiments using a hard X-ray quarter-wave plate, at both polychromatic dispersive and conventional monochromatic optics, in combination with synchronous data acquisition. The switching frequency waveform is fed into a lock-in amplifier to detect and amplify the XMCD signal. The results on a reference sample demonstrate an improvement in data quality and acquisition time. The instrumentation successfully generated 98% of CP X-rays switching the beam helicity at 13 Hz, with the possibility of faster helicity switching once it is installed at the new Brazilian fourth-generation source, SIRIUS.

Pressure Tuning of Superconductivity of LaPt4Ge12 and PrPt4Ge12 Single Crystals.

We carried out electrical resistivity and X-ray diffraction (XRD) studies on the filled skutterudite superconductors LaPt4Ge12 and PrPt4Ge12 under hydrostatic pressure. The superconducting transition temperature Tc is linearly suppressed upon increasing pressure, though the effect of pressure on Tc is rather weak. From the analysis of the XRD data, we obtain bulk moduli of B=106 GPa and B=83 GPa for LaPt4Ge12 and PrPt4Ge12, respectively. The knowledge of the bulk modulus allows us to compare the dependence of Tc on the unit-cell volume from our pressure study directly with that found in the substitution series La1-xPrxPt4Ge12. We find that application of hydrostatic pressure can be characterized mainly as a volume effect in LaPt4Ge12 and PrPt4Ge12, while substitution of Pr for La in La1-xPrxPt4Ge12 yields features going beyond a simple picture.