Yukio Hinatsu

Reversible Mechanochromic Luminescence of [(C6F5Au)2(μ-1,4-Diisocyanobenzene)]

Reversible mechanochromic luminescence of [(C6F5Au)2(mu-1,4-diisocyanobenzene)] is reported. Grinding of the complex induced a photoluminescent color change, which was restored by exposure to a solvent. This cycle was repeated 20 times with no color degradation in the emissions. Their optical properties, X-ray crystallographic analysis, IR, and XRD measurements strongly suggested that the change in the molecular arrangement is responsible for this mechanochromic property. Intermolecular aurophilic bondings presumably play a key role in the altered emission.

Crystal structures and magnetic properties of ordered perovskites Sr2LnRuO6 (Ln = Eu-Lu)

The perovskite-type compounds Sr2LnRuO6 (Ln = Eu-Lu) have been synthesized, and their crystal structures and magnetic properties have been investigated. Powder x-ray diffraction measurements and the Rietveld analysis show that they are monoclinic with space group P21/n and that Ln3+ and Ru5+ ions are structurally ordered. These compounds show complex magnetic transitions at low temperatures. These transitions are considered to be antiferromagnetic ones from large negative Weiss constants. Below the transition temperatures, there is a large difference in the temperature dependence of the magnetic susceptibility measured under the zero-field cooled condition and under the field cooled condition, which shows the existence of a weak ferromagnetic moment associated with the antiferromagnetism.

Remarkable Magneto-Optical Properties of Europium Selenide Nanoparticles with Wide Energy Gaps

The enhanced magneto-optical properties of nanoscaled lanthanide chalogenide semiconductors which have a wide energy gap were observed at around 500 nm for the first time. The nanoscaled semiconductors, Eu(1-x)Se nanoparticles 1 (cubic shapes) and 2 (spherical shapes), were synthesized by the thermal reduction of Eu(III) ion with organic ligands containing Se atoms. The resulting Eu(1-x)Se nanoparticles were characterized by X-ray diffraction, high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, superconducting quantum interference devices magnetometer, and microwave induced plasma atomic emission spectroscopy measurements. The particle grain sizes of 1 and 2 were estimated to be 11 and 20 nm, respectively. The concentration-normalized Veldet constants (the magnitude of the Faraday effect) of Eu(1-x)Se nanoparticles were much larger than those of corresponding bulk EuSe and EuS nanoparticles.

Metal--Insulator Transitions in Pyrochlore Oxides Ln2Ir2O7

We report the physical properties of Ln 2 Ir 2 O 7 ( Ln = Nd, Sm, Eu, Gd, Tb, Dy, and Ho), which exhibit metal–insulator transitions (MITs) at different temperatures. The transition temperature T MI increases with a reduction in the ionic radius of Ln . The ionic radius boundary for MITs in Ln 2 Ir 2 O 7 lies between Ln = Pr and Nd. MITs in Ln 2 Ir 2 O 7 have some common features. They are second-order transitions. Under the field cool condition, a weak ferromagnetic component (∼10 -3 µ B /f.u.) caused by Ir 5 d electrons is observed below T MI . The entropy associated with MITs for Ln = Nd, Sm, and Eu is estimated to be 0.47, 2.0, and 1.4 J/(K·mole), respectively. The change in entropy is much smaller than 2 R ln 2 [11.5 J/(K·mole)] expected in a magnetic transition due to localized moments of S = 1/2. The feature of continuous MITs in Ln 2 Ir 2 O 7 is discussed.

Specific Heat Study on Sm-based Filled Skutterudite Phosphides SmT4P12(T=Fe, Ru and Os)

Sm-based filled skutterudite phosphides SmFe 4 P 12 , SmRu 4 P 12 and SmOs 4 P 12 synthesized at high temperatures and high pressures have been studied by specific heat measurements in magnetic fields. SmFe 4 P 12 shows an anomaly at 1.6 K attributed to a ferromagnetic transition. SmRu 4 P 12 shows a metal–insulator transition at 16 K. This transition consists of two successive transitions, which suggests orbital and antiferromagnetic orderings. SmOs 4 P 12 shows a sharp anomaly at 4.5 K due to an antiferromagnetic ordering. We discuss the characteristic behavior of those phase transitions and the crystalline electric field state in Sm T 4 P 12 ( T =Fe, Ru and Os). Interestingly, the magnetic entropy of SmFe 4 P 12 have only 0.16 R ln 2 below the ferromagnetic ordering temperature. This suggests a strong spin fluctuation effect. On the other hand, the variation of magnetic entropy in SmRu 4 P 12 and SmOs 4 P 12 reaches to nearly R ln 4 below the ordering temperature.

Metal-insulator transition in pyrochlore iridates Ln2Ir2O7 (Ln = Nd, Sm, and Eu)

We report that Ln 2 Ir 2 O 7 for Ln = Nd, Sm, and Eu have metal–insulator transitions (MITs) at 36, 117, and 120 K, respectively. Their electrical resistivities and thermoelectric powers are not discontinuous and exhibit no thermal hysteresis at their transition temperatures T MI , indicating second-order phase transitions. In this letter, we focus on the MIT of Sm 2 Ir 2 O 7 . The specific heat and the magnetic susceptibility show a clear anomaly at T MI . These results indicate that this MIT involves a magnetic ordering produced by 5 d electrons in Ir.

Magnetic properties of the antiferromagnetic double perovskite Ba2PrRuO6

The ordered perovskite compound Ba2PrRuO6 is prepared and its magnetic properties are investigated. The Rietveld analysis of the neutron diffraction profiles measured at 150 K shows that the Pr3+ and Ru5+ ions are arranged with regularity over the six-coordinate B sites of the perovskite ABO3 and that Ba2PrRuO6 belongs to space group P21/n, with a = 6.0063(5), b = 5.9863(4), c = 8.4677(7) A and 90.04(2)°. The magnetic susceptibility and the heat capacity measurements show that this compound transforms to an antiferromagnetic state below 117 K. From the neutron diffraction patterns measured at 7 K, the magnetic structure is determined to be of Type I and the magnetic moments of Pr3+ and Ru5+ are estimated to be 2.2(1) and 2.0(2) µB, respectively. Their values are discussed on the basis of theoretical calculations for the crystal field splitting.

Magnetic susceptibility of LiUO3

Abstract LiUO3 was prepared, and its magnetic susceptibility was measured in the 4.2–300 K temperature range. Magnetic transition occurred at 16.9 K, and below this temperature large field dependence of the magnetic susceptibility was observed. The crystal field parameters of LiUO3 were determined from the optical absorption spectrum of U5+ doped in LiNbO3. The susceptibility and the g-value of electron paramagnetic resonance were calculated and compared with the experimental results.

Crystal structures and magnetic properties of ordered perovskites A2R3+Ir5+O6 (A=Sr, Ba; R=Sc, Y, La, Lu)

Abstract The ordered perovskite-type compounds A 2 RIrO 6 (A=Sr, Ba; R=Sc, Y, Lu, La), with the exception of Sr 2 LaIrO 6 , were prepared. Using the Rietveld method, their crystal structures were assigned to be monoclinic (space group P2 1 /n ) with a fully ordered arrangement between R and Ir ions. For Sr 2 ScIrO 6 and Ba 2 ScIrO 6 , small amounts of disordered arrangements between Sc and Ir ions were found. The magnetic susceptibilities of these compounds show paramagnetic behavior down to 4.5 K. The magnetic behavior for these compounds is explained by Kotani’s theory and the spin–orbit coupling constants for the Ir(V) ion were calculated.

Emergence of Magnetic Long-range Order in Frustrated Pyrochlore Nd2Ir2O7 with Metal–Insulator Transition

In this study, we performed powder neutron diffraction and inelastic scattering measurements of frustrated pyrochlore Nd 2 Ir 2 O 7 , which exhibits a metal–insulator transition at a temperature T MI of 33 K. The diffraction measurements revealed that the pyrochlore has an antiferromagnetic long-range structure with propagation vector q 0 of (0,0,0) and that it grows with decreasing temperature below 15 K. This structure was analyzed to be of the all-in all-out type, consisting of highly anisotropic Nd 3+ magnetic moments of magnitude 2.3±0.4µ B , where µ B is the Bohr magneton. The inelastic scattering measurements revealed that the Kramers ground doublet of Nd 3+ splits below T MI . This suggests the appearance of a static internal magnetic field at the Nd sites, which probably originates from a magnetic order consisting of Ir 4+ magnetic moments. Here, we discuss a magnetic structure model for the Ir order and the relation of the order to the metal–insulator transition in terms of frustration.