The structural, transport, and magnetic properties of Yb-filled skutterudites YbyFexCo4−xSb12 synthesized under high pressure

The effects of Fe-substitution on partially Yb filled skutterudites YbyFexCo4-xSb12 are presented from the viewpoint of crystal structure and thermoelectric, magnetic, and transport properties. A series of polycrystalline n-type YbyFexCo4-xSb12 (0.21 ≤ y ≤ 0.47, 0 ≤ x ≤ 0.76) samples were prepared using a high-pressure and high-temperature method. X-ray diffraction data suggest that all the compounds are high-purity skutterudites. For the YbyFexCo4-xSb12 with Yb content higher than 0.29 and Fe content lower than 1, the lattice constant shows a saturated behavior despite the change in the Yb/Fe content. Rietveld refinement based on the synchrotron radiation X-ray data implies that the rectangular Sb4 ring is transformed into square with increasing Yb content and/or Fe substitution content. The Yb valence gradually decreases as the Fe content increases from magnetic susceptibility analysis. According to the specific heat analysis, higher Yb filling benefits the lower Debye temperature while the Fe substitution leads to an increased Debye temperature. The Einstein temperature decreased with increasing Yb filling fraction, but Fe substitution for the Co site does not change the Einstein temperature further. Fe-substitution causes the reduction of total thermal conductivity κ, which mainly originates from the decrease of electron thermal conductivity contribution. The resistivity, Seebeck coefficient, thermal conductivity, and figure of merit (ZT) were effectively tuned due to the optimization of the carrier concentration. At the same carrier concentration, the hall mobility was decreased by Fe substitution. The proper Fe substitution content (0.2 in Yb0.25Fe0.2Co3.8Sb12) can result in a relatively high effective mass

High-pressure and high-temperature synthesis of heavy lanthanide sesquisulfides Ln2S3 ( Ln=Yb and Lu)

Detailed pressure-temperature phase diagrams of heavy lanthanide sesquisulfides Ln2S3 (Ln = Yb and Lu) have been investigated by in-situ x-ray diffraction experiments under high pressure and high temperature using synchrotron radiation and multi-anvil press. Based on the results of the in-situ observation, the single γ-phase (Th3P4-type structure, I3d) samples of Ln2S3 (Ln = Yb and Lu) have been synthesized under high pressure. The physical properties of the compounds were studied by electrical resistivity, specific heat, and magnetic susceptibility measurements between 2 K and 300 K

Superlattice formation lifting degeneracy protected by non-symmorphic symmetry through a metal-insulator transition in RuAs

The single crystal of RuAs obtained by Bi-flux method shows obvious successive metal-insulator transitions at T_MI1~255 K and T_MI2~195$ K. The X-ray diffraction measurement reveals a formation of superlattice of 3x3x3 of the original unit cell below T_MI2, accompanied by a change of the crystal system from the orthorhombic structure to the monoclinic one. Simple dimerization of the Ru ions is nor seen in the ground state. The multiple As sites observed in nuclear quadrupole resonance (NQR) spectrum also demonstrate the formation of the superlattice in the ground state, which is clarified to be nonmagnetic. The divergence in 1/T_1 at T_MI1 shows that a symmetry lowering by the metal-insulator transition is accompanied by strong critical fluctuations of some degrees of freedom. Using the structural parameters in the insulating state, the first principle calculation reproduces successfully the reasonable size of nuclear quadrupole frequencies for the multiple As sites, ensuring the high validity of the structural parameters. The calculation also gives a remarkable suppression in the density of states (DOS) near the Fermi level, although the gap opening is insufficient. A coupled modulation of the calculated Ru d electron numbers and the crystal structure proposes a formation of charge density wave (CDW) in RuAs. Some lacking factors remain, but it shows that a lifting of degeneracy protected by the non-symmorphic symmetry through the superlattice formation is a key ingredient for the metal-insulator transition in RuAs.Comment: 10 pages, 10 figure

Low-temperature oxyanion-accelerated vinylcyclopropane-cyclopentene rearrangement. Reaction of 2-(2-(trimethylsilyl)-ethenyl)cyclopropyl acetates with methyl lithium

Reactions of four diastereomeric 2-(2-(trimethylsilyl)ethenyl)cyclopropyl acetates 7, derived from enol silyl ether 4 and Fischer carbene complex 6, with 2.2 equiv of MeLi at -80 ° to -30 °C afforded cyclopentenol 8 as a single diastereomer and acyclic enol silyl ethers 9 via the corresponding cyclopropanolates in ratios depending on the vinylsilane geometry. Predominant formation of 8 over 9 from (Z)-7 irrespective of the stereochemistry at C-1 was observed. This is the first example of oxyanion-accelerated vinylcyclopropane-cyclopentene rearrangement which proceeds at unprecedentedly low temperatures

Systematic Study of Lattice Specific Heat of Filled Skutterudites

The lattice specific heat C lat of La-based filled skutterudites La T 4 X 12 ( T = Fe, Ru and Os; X = P, As, and Sb) has been systematically studied, and both the Debye temperature Θ D and the Einstein temperature Θ E of La T 4 X 12 were carefully estimated. We confirmed that a correlation exists between Θ D and the reciprocal of the square root of average atomic mass for La T 4 P 12 , La T 4 As 12 , and La T 4 Sb 12 . The Θ D of filled skutterudites was found to depend mainly on the nature of the species X forming the cage. The temperature dependence of C lat / T 3 for La T 4 X 12 exhibited a large broad maximum at low temperatures (10–30 K), which suggests a nearly dispersionless low-energy optical mode characterized by Einstein specific heat. Since no such broad maximum exists for the unfilled skutterudite RhP 3 , the low-energy optical modes are associated with vibration involving La ions in the X 12 cage (the so-called “guest ion modes”). The Θ E of filled skutterudites was found to roughly correspond to the energy of low-energy guest ion optical modes. Furthermore, a good correlation was shown to exist between Θ E and r R–X - r R3+ , where r R–X is the R – X distance and r R3+ is the effective ionic radius of R 3+ . As r R–X - r R3+ increased, Θ E was found to decrease

X-Ray Diffraction Study of CeT2Al10 (T = Ru, Os) at Low Temperatures and under Pressures

We have carried out a powder X-ray diffraction investigation on antiferromagnetic Kondo semiconductorsCeRu2Al10 and CeOs2Al10 at low temperatures and under high pressures as well as the structural investigationon single crystal of these compounds. The results of powder X-ray studies of CeRu2Al10 and CeOs2Al10 indicatethat these compounds do not have structural transition at its antiferromagnetic ordering temperature. The resultsof single crystal structural refinement indicate that the b-axis of this crystal structure is insensitive not only topressure but also to temperature and that the effect of cooling to Ce–Ce distance for CeRu2Al10 is the same asthat for CeOs2Al10

3,11-Diaminodibenzo[a,j]phenazine: Synthesis, Properties, and Applications to Tröger's Base-Forming Ladder Polymerization

This is the accepted version of the following article: Izumi S., Inoue K., Nitta Y., et al. 3,11-Diaminodibenzo[a,j]phenazine: Synthesis, Properties, and Applications to Tröger's Base-Forming Ladder Polymerization. Chemistry - A European Journal 29, e202202702 (2023), which has been published in final form at https://doi.org/10.1002/chem.202202702. This article may be used for non-commercialpurposes in accordance with the Wiley Self-ArchivingPolicy. [https://authorservices.wiley.com/author-resources/Journal-Authors/licensing/self-archiving.html]A new class of diamino-substituted π-extended phenazine compound was synthesized, and its photophysical properties were investigated. The U-shaped diaminophenazine displayed photoluminescence in solution with moderate quantum yield. The diamino aromatic compound was found applicable to the poly-condensation with formaldehyde to form Tröger's base ladder polymer. The obtained microporous ladder polymer features high CO2 adsorption selectivity against N2, most likely due to the presence of basic nitrogen atoms in the phenazine rings

Magnetic properties of new filled skutterudite compound BaFe4As12

The magnetic, electrical and thermal properties of a new As-based alkaline-earth-filled skutterudite compound BaFe4As12 prepared under high pressure have been studied at low temperatures. The temperature dependence of the electrical resistivity for BaFe4As12 reveals a metallic behavior. Any anomalies accompanied by phase transition were not observed down to 2K. A broad maximum of magnetic susceptibility around 50 K and a large electronic specific heat coefficient of 62 mJ/molK2 suggest that BaFe4As12 is a nearly ferromagnetic metal with spin fluctuations of Fe 3d electrons

High-pressure Synthesis and Physical Properties of New Filled Skutterudite Compound BaOs4P12

We have succeeded in synthesizing samples of new filled skutterudite compound BaOs4P12 using the high-pressure synthesis technique. The physical properties of the compound are reported for the first time. The electrical resistivity decreases with decreasing temperature, and drop sharply around 1.8K. This indicates that BaOs4P12 is a new superconductor. Before the high-pressure synthesis, using synchrotron radiation x-ray, we tried to observe synthesizing processes of BaOs4P12 in-situ at high temperature and high pressure to obtain the optimum condition for synthesis

First-order phase transition to a nonmagnetic ground state in nonsymmorphic NbCrP

We report the discovery of a first-order phase transition at around 125 K in NbCrP, which is a nonsymmorphic crystal with the Pnma space group. From the resistivity, magnetic susceptibility, and nuclear magnetic resonance measurements using crystals made by the Sn-flux method, the high-temperature (HT) phase is characterized to be metallic with a non-negligible magnetic anisotropy. The low-temperature (LT) phase is also found to be a nonmagnetic metallic state with a crystal of lower symmetry. In the LT phase, the spin susceptibility is reduced by ∼30% from that in the HT phase, suggesting that the phase transition is triggered by the electronic instability. The possible origin of the phase transition in NbCrP is discussed based on the electronic structure by comparing it with those in other nonsymmorphic compounds, RuP and RuAs