New molecular magnetic metals: κ-(BDH-TTP)4CuCl4·(H2O)n and κ-(BDH-TTP)2[CuCl4]0.67·(H2O)0.33 (BDH-TTP is 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene)

New radical cation salts based on 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP), viz., κ-(BDH-TTP)₄CuCl₄·(H₂O) _n (1) and κ-(BDH-TTP)₂[CuCl₄]_0.67· ·(H₂O)_0.33 (2), were synthesized and structurally characterized. Single crystals were prepared by the electrochemical oxidation of BDH-TTP under galvanostatic conditions. The X-ray diffraction study showed that the salts have layered structures characterized by the presence of κ-type BDH-TTP conducting layers. These layers alternate with the complex anions composed of [CuCl₄]²⁻ units and water molecules. Both salts exhibit the temperature dependence of the metallic conductivity down to 4.2 K. Spin-spin antiferromagnetic correlations in the Cu²⁺ subsystem were observed in the crystals of 2.     

Palladium-catalyzed asymmetric synthesis of axially chiral allenylsilanes and their application to SE2' chirality transfer reactions

Stepwise application of the Pd-catalyzed S(N)2' reaction and the desilylative S(E)2' reaction to the ambivalent 2-bromo-1-silyl-1,3-dienes provides a novel route to the highly enantioselective construction of tertiary and quaternary propargylic stereogenic centers via axially chiral allenylsilanes.     

Effects of indium doping on the superconducting properties of YBa2Cu3Oy sintered compounds and thin films

We investigated the effects of indium doping on the superconducting properties of YBCO sintered samples and thin films. In₂O₃-doped YBCO and YBa₂Cu_3−xIn_xO_y sintered samples showed a gradual decrease in the critical temperature (T_c) with increasing indium content; however, a T_c value above 80 K was maintained even up to 30 vol.% addition and x = 0.4, respectively. Ba₃Cu₃In₄O₁₂ was detected by X-ray diffractometry and energy-dispersive X-ray spectroscopy as a reaction product for both sintered samples. The normalized J_c under a magnetic field of 0.1 T showed a maximum at x = 0.3. Indium-doped YBCO films prepared by pulsed laser deposition showed a similar dependence of T_c on indium content as the sintered samples.     

Current transport property in GdBCO coated conductor with artificial pinning centers in a wide range of temperature,magnetic field up to 27 T,and field angle

We have investigated current transport property in Gd₁Ba₂Cu₃O_7−δ coated conductor with artificial pinning centers in a wide range of temperature, magnetic field, B up to 27 T, and field angle. Due to the additional c-axis correlated pins, critical current density, J_c in B//c was enhanced and the improvement was observed in wide range of B. On the other hand, around B⊥c below 65 K, the angular dependence of n-value showed a valley-like behavior, although the J_c was increasing. In addition, the temperature dependence of the pinning force density defined as J_c × B was not scaled on an expected master curve. These results indicate the pinning in B⊥c is governed by different mechanism below 65 K and high magnetic field.     

Magnetic Field Effects on the Photoinduced Electron-Transfer Reactions in a Ruthenium Porphyrin–C60 Ligand Complex

Magnetic field effects (MFEs) on a photoinduced electron-transfer reaction in a semi-rigid linked system (RuP–C₆₀) were examined in toluene and o-dichlorobenzene. The transient absorption spectra indicated that the photogenerated biradical produced by an intramolecular electron-transfer reaction was observed only in o-dichlorobenzene. The decay rate constants (k _d) for the biradical decreased steeply at lower magnetic fields (≤0.06 T) and rapidly recovered at 0.08 T. The k _d value was observed to decrease gradually above 0.2 T. The MFEs strongly indicated the formation of the singlet-born biradical for RuP–C₆₀. The dip in the MFE at 0.06 T was ascribed to the S–T level crossing mechanism. The MFEs above 0.2 T can be explained by a spin–spin relaxation mechanism due to the anisotropic Zeeman interaction being related to the exchange interaction.     

X-ray photoelectron and X-ray absorption spectroscopic study on β-FeSi2 thin films fabricated by ion beam sputter deposition

A combination of X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) using synchrotron radiation is applied to clarify surface chemical states of β-FeSi₂ films fabricated by an ion-beam sputtering deposition method. The differences in the chemical states of the films fabricated at substrate temperatures of 873, 973 and 1173 K are investigated. For the film fabricated at 873 K, Si 2p XPS spectra indicate the formation of a relatively thicker SiO₂ layer. In addition, Fe L-edge XAS spectra exhibit the formation of FeSi_2−X by preferential oxidation of Si or the presence of unreacted Fe. The results for the film fabricated at 1173 K imply the existence of FeSi₂ with α and ? phases. In contrast, the results for the film fabricated at 973 K indicate the formation of relatively homogeneous β-FeSi₂. These imply that the relatively excellent crystal property of the film fabricated at 973 K is due to the formation of homogeneous β-FeSi₂. As a conclusion, the combination of XPS and XAS using synchrotron radiation is a powerful tool to elucidate the surface chemical states of thin films.     

Asymmetric Suzuki–Miyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin

You oughta use water : Broad functional‐group (FG) tolerance was observed for the title coupling of aryl halides (X=Cl, Br, I) and aryl boronic acids to give biaryl compounds with up to 94 % ee. The chiral imidazoindole phosphine–palladium catalyst supported on an amphiphilic polystyrene–poly(ethylene glycol) (PS–PEG) resin could be recycled readily.