Pressure Dependence of the Structural and Superconducting Properties of the Bi-Based Superconductor Bi2Pd3Se2.

The structural and superconducting properties of the Bi-based compound Bi2Pd3Se2 were investigated over a wide pressure range. The prepared Bi2Pd3Se2 sample was a superconductor with a superconducting transition temperature, Tc, of approximately 3.0 K, which differed from a previous report (Tc of less than 1.0 K). At ambient pressure, the powder X-ray diffraction (XRD) pattern of the Bi2Pd3Se2 sample was consistent with that previously reported for Bi2Pd3Se2. The Rietveld method was used to refine the crystal structure, which had a space group of C2/m (No. 12), as reported previously. This compound showed no clear anomaly due to the charge-density-wave (CDW) transition, as seen from the temperature dependence of magnetic susceptibility. However, the temperature dependence of electrical resistivity indicated a clear anomaly, presumably because of the CDW transition in the low-pressure range; the CDW transition temperature was approximately 230 K. The XRD patterns of the Bi2Pd3Se2 sample were measured at 0.160-22.7 GPa, and the patterns were well analyzed by both the Le Bail and Rietveld refinement methods, showing no structural phase transitions in the above pressure range. The pressure dependence of Tc of Bi2Pd3Se2 was recorded based on the temperature dependence of the electrical resistance, which showed an almost constant Tc at 0-13.7 GPa, and the Tc-pressure (p) behavior was fully discussed.

Helimagnetic Structure and Heavy-Fermion-Like Behavior in the Vicinity of the Quantum Critical Point in Mn_{3}P.

Antiferromagnet Mn_{3}P with Neel temperature T_{N}=30 K is composed of Mn tetrahedrons and zigzag chains formed by three inequivalent Mn sites. Due to the nearly frustrated lattice with many short Mn-Mn bonds, competition of the exchange interactions is expected. We here investigate the magnetic structure and physical properties including pressure effect in single crystals of this material, and reveal a complex yet well-ordered helimagnetic structure. The itinerant character of this materials is strong, and the ordered state with small magnetic moments is easily suppressed under pressure, exhibiting a quantum critical point at ∼1.6 GPa. The remarkable mass renormalization, even in the ordered state, and an incoherent-coherent crossover in the low-temperature region, characterize an unusual electronic state in Mn_{3}P, which is most likely effected by the underlying frustration effect.

Chemical analysis of superconducting phase in K-doped picene.

Potassium-doped picene (K3.0picene) with a superconducting transition temperature (T C) as high as 14 K at ambient pressure has been prepared using an annealing technique. The shielding fraction of this sample was 5.4% at 0 GPa. The T C showed a positive pressure-dependence and reached 19 K at 1.13 GPa. The shielding fraction also reached 18.5%. To investigate the chemical composition and the state of the picene skeleton in the superconducting sample, we used energy-dispersive x-ray (EDX) spectroscopy, MALDI-time-of-flight (MALDI-TOF) mass spectroscopy and x-ray diffraction (XRD). Both EDX and MALDI-TOF indicated no contamination with materials other than K-doped picene or K-doped picene fragments, and supported the preservation of the picene skeleton. However, it was also found that a magnetic K-doped picene sample consisted mainly of picene fragments or K-doped picene fragments. Thus, removal of the component contributing the magnetic quality to a superconducting sample should enhance the volume fraction.

Emergence of double-dome superconductivity in ammoniated metal-doped FeSe.

The pressure dependence of the superconducting transition temperature (Tc) and unit cell metrics of tetragonal (NH3)yCs0.4FeSe were investigated in high pressures up to 41 GPa. The Tc decreases with increasing pressure up to 13 GPa, which can be clearly correlated with the pressure dependence of c (or FeSe layer spacing). The Tc vs. c plot is compared with those of various (NH3)yMxFeSe (M: metal atoms) materials exhibiting different Tc and c, showing that the Tc is universally related to c. This behaviour means that a decrease in two-dimensionality lowers the Tc. No superconductivity was observed down to 4.3 K in (NH3)yCs0.4FeSe at 11 and 13 GPa. Surprisingly, superconductivity re-appeared rapidly above 13 GPa, with the Tc reaching 49 K at 21 GPa. The appearance of a new superconducting phase is not accompanied by a structural transition, as evidenced by pressure-dependent XRD. Furthermore, Tc slowly decreased with increasing pressure above 21 GPa, and at 41 GPa superconductivity disappeared entirely at temperatures above 4.9 K. The observation of a double-dome superconducting phase may provide a hint for pursuing the superconducting coupling-mechanism of ammoniated/non-ammoniated metal-doped FeSe.

Hindered rotation of methane molecules in the one-dimensional nanochannel of a porous coordination polymer.

The crystal structure of a microporous coordination polymer with adsorbed methane gas was determined by in situ synchrotron powder diffraction of the gas adsorption and the MEM (maximum entropy method)/Rietveld method. Methane molecules were found to be adsorbed forming a one-dimensional array in the nanochannels of the polymer. The MEM charge density distribution of the adsorbed methane molecules indicated some protrusions which were not observed in that of a spherical atom of adsorbed argon. This was interpreted as a mixed distribution of two uniaxially rotating molecules with different pivotal axes. The methane molecules displayed hindered rotation depending on the shape of the nanopore surface. This result indicates the capability to control the molecular arrangement and orientation by the adsorption of gas molecules on the precisely designed nanopores of coordination polymers.

Formation and characterization of crystalline molecular arrays of gas molecules in a 1-dimensional ultramicropore of a porous copper coordination polymer.

Molecules and atoms confined in a nanospace may have properties distinctly different from those of the bulk fluid, owing to the formation of a specific molecular array characteristic of nanospace. In situ synchrotron powder X-ray diffraction measurements have been used to observe confined guest molecules such as N2, O2, Ar, and CH4 in the well-regulated ultramicropore of a copper coordination polymer, 1 ([Cu2(pzdc)2pyz]: pzdc = 2,3-pyrazinedicarboxylate and pyz = pyrazine). The obtained crystal structures indicate that guest molecules are confined in a linear fashion to form crystalline-like regular ordered arrays, in contrast to the situation in the gas and liquid state, even at temperatures above the boiling point, and the ordered arrays are characteristic of the kind of gas molecule and the geometrical and potential properties of the ultramicropore of 1.

Highly controlled acetylene accommodation in a metal-organic microporous material.

Metal-organic microporous materials (MOMs) have attracted wide scientific attention owing to their unusual structure and properties, as well as commercial interest due to their potential applications in storage, separation and heterogeneous catalysis. One of the advantages of MOMs compared to other microporous materials, such as activated carbons, is their ability to exhibit a variety of pore surface properties such as hydrophilicity and chirality, as a result of the controlled incorporation of organic functional groups into the pore walls. This capability means that the pore surfaces of MOMs could be designed to adsorb specific molecules; but few design strategies for the adsorption of small molecules have been established so far. Here we report high levels of selective sorption of acetylene molecules as compared to a very similar molecule, carbon dioxide, onto the functionalized surface of a MOM. The acetylene molecules are held at a periodic distance from one another by hydrogen bonding between two non-coordinated oxygen atoms in the nanoscale pore wall of the MOM and the two hydrogen atoms of the acetylene molecule. This permits the stable storage of acetylene at a density 200 times the safe compression limit of free acetylene at room temperature.

Guest shape-responsive fitting of porous coordination polymer with shrinkable framework.

In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds.

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework.

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

Formation of a one-dimensional array of oxygen in a microporous metal-organic solid.

We report the direct observation of dioxygen molecules physisorbed in the nanochannels of a microporous copper coordination polymer by the MEM (maximum entropy method)/Rietveld method, using in situ high-resolution synchrotron x-ray powder diffraction measurements. The obtained MEM electron density revealed that van der Waals dimers of physisorbed O2 locate in the middle of nanochannels and form a one-dimensional ladder structure aligned to the host channel structure. The observed O-O stretching Raman band and magnetic susceptibilities are characteristic of the confined O2 molecules in one-dimensional nanochannels of CPL-1 (coordination polymer 1 with pillared layer structure).