Organometallic Molecular Wires with Thioacetylene Backbones,trans-{RS-(C≡C)n}2Ru(phosphine)4: High Conductance through Non-Aromatic Bridging Linkers

In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C₆H₁₃S, p-tert-Bu−C₆H₄S), trans-{RS−(C≡C)_n}₂Ru(dppe)₂ (n=1 ( 1^R ), 2 ( 2^R ); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C₆H₁₃S−C≡C)₂Ru{P(OMe)₃}₄ 3^hex ] are reported. Scanning tunneling microscope break-junction study has revealed conductance of the organometallic molecular wires with the thioacetylene backbones higher than that of the related organometallic wires having arylethynylruthenium linkages with the sulfur anchor groups, trans-{p-MeS−C₆H₄-(C≡C)_n}₂Ru(phosphine)₄ 4 ⁿ (n=1, 2) and trans-(Th−C≡C)₂Ru(phosphine)₄ 5 (Th=3-thienyl). It should be noted that the molecular junctions constructed from the butadiynyl wire 2^R , trans-{ Au −RS−(C≡C)₂}₂Ru(dppe)₂ ( Au : gold metal electrode), show conductance comparable to that of the covalently linked polyynyl wire with the similar molecular length, trans-{ Au −(C≡C)₃}₂Ru(dppe)₂ 6³ . The DFT non-equilibrium Green's function (NEGF) study supports the highly conducting nature of the thioacetylene molecular wires through HOMO orbitals.     

Structure and Electron Transport at Metal Atomic Junctions Doped with Dichloroethylene

The front cover artwork was provided by the group of Prof. Nishino, Tokyo Institute of Technology. The image depicts the investigation of the structure and electron transport of the Au, Ag, Cu, Ni, Fe, and Pd atomic junctions doped with dichloroethylene. Read the full text of the Article at 10.1002/cphc.201900988 .     

Mn(III)-based reaction of alkenes with quinolinones. Formation of peroxyquinolinones and quinoline-related derivatives

The reactions of 1,1-disubstituted alkenes with 4-hydroxyquinolin-2(1H)-ones under both Mn(III)-catalyzed aerobic oxidation conditions at room temperature and Mn(III)-mediated oxidation conditions at reflux temperature are described. The Mn(III)-catalyzed aerobic oxidation afforded bis(hydroperoxyethyl)quinolinones and azatrioxa[4.4.3]propellanes, while the oxidation with Mn(OAc)₃·2H₂O produced furo[3,2-c]quinolin-4-one analogues. The existence of a substituent at the 3-position of the 4-hydroxyquinolin-2(1H)-ones prevented a double reaction with the alkenes, and (endoperoxy)quinolinones and/or (hydroperoxyethyl)quinolinones were obtained under the Mn(III)-catalyzed aerobic conditions, while furo[3,2-c]quinolinone hemiacetals and vinylquinolinones were selectively produced under the Mn(III)-mediated oxidation conditions depending on the reaction temperature and times. Cyclic assembly of quinolinone-related 1,3-dicarbonyl compounds such as dihydropyridinones, pyranones, and dimedone derivatives was also examined under elevated temperature conditions.     

Measurements of residual stress in semi-insulating GaAs by Cr-related luminescence lines

We have measured systematically the Cr-related zero-phonon lines in the 0.839 eV region in a series of plastically-bent semi-insulating GaAs:Cr with compressive or tensile stress along various bending axes. As a result, it has been found that the residual stress in semi-insulating GaAs:Cr wafers can be sensitively characterized from a splitting and energy shift of the 0.839 eV Cr-related luminescence lines in the low-temperature photoluminescence spectra. Furthermore, we have applied this method to the characterization of the interface stress of OMVPE-grown ZnSe/GaAs:Cr heterostructure and found that anomalous stress exists at the ZnSe/GaAs interface, which is inconsistent with stress predicted by the lattice mismatch of the heterojunctions.     

Femtosecond Diffuse-Reflectance Spectroscopy of Various Commercially Available TiO2 Powders

The transient absorption properties of several commercially available TiO₂ photocatalysts were investigated by femtosecond diffuse-reflectance spectroscopy. Using femtosecond diffuse-reflectance spectroscopy, the quantities and rates of the initial trapping processes of holes and electrons generated by the photoexcitation of TiO₂ photocatalysts were investigated. It was found that the total amounts of trapped electrons for the pure-anatase and pure-rutile TiO₂ became smaller with increasing particle size, but increased again when the particles’ diameters were larger than 50 nm. The anatase–rutile mixed TiO₂ photocatalysts were found to have smaller amounts of trapped electrons compared with pure-anatase and pure-rutile TiO₂ photocatalysts. The lifetimes of trapped holes of various TiO₂ photocatalysts were also investigated, and it was found that the lifetimes were proportional to the anatase–rutile mixed ratios.     

Exploring leptonic CP violation by reactor and neutrino superbeam experiments

We point out the possibility that reactor measurement of θ₁₃, when combined with high-statistics ν_e appearance accelerator experiments, can detect leptonic CP violation. Our proposal is based on a careful statistical analysis under reasonable assumptions on systematic errors, assuming 2 years running of the neutrino mode J-PARC → Hyper-Kamiokande experiment and a few years running of a reactor experiment with 100 t detectors at the Kashiwazaki–Kariwa nuclear power plant. We show that the method can be arranged to be insensitive to the intrinsic parameter degeneracy but is affected by the one due to unknown sign of Δm²₃₁.     

Symmetrization of Nonsymmetric Macdonald Polynomials and Macdonald's Inner Product Identities

We study the Macdonald polynomials that give eigenstates of some quantum many-body system with long-range interactions. Scalar products of the nonsymmetric Macdonald polynomials are algebraically evaluated through their Rodrigues-type formulas. We present a new proof of Macdonald's inner product identities without recourse to the shift operators; that is, we calculate square norms of the Macdonald polynomials through Weyl-symmetrization of those of the nonsymmetric Macdonald polynomials.