Electronic state of a conducting single molecule magnet based on Mn-salen type and Ni-dithiolene complexes

The electrochemical oxidation of an acetone solution containing [Mn(III) (5-MeOsaltmen)(H(2)O)](2)(PF(6))(2) (5-MeOsaltmen(2-) = N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)) and (NBu(4))[Ni(dmit)(2)] (dmit(2-) = 2-thioxo-1,3-dithiole-4,5-dithiolate) afforded a hybrid material, [Mn(5-MeOsaltmen)(acetone)](2)[Ni(dmit)(2)](6) (1), in which [Mn(2)](2+) single-molecule magnets (SMMs) with an S(T) = 4 ground state and [Ni(dmit)(2)](n-) molecules in a charge-ordered state (n = 0 or 1) are assembled in a layer-by-layer structure. Compound 1 crystallizes in the triclinic space group P1 with an inversion center at the midpoint of the Mn···Mn dimer. The [Mn(2)](2+) unit has a typical nonplanar Mn(III) dimeric core and is structurally consistent with previously reported [Mn(2)] SMMs. The six [Ni(dmit)(2)](n-) (n = 0 or 1) units have a square-planar coordination geometry, and the charge ordering among them was assigned on the basis of ν(C═C) in IR reflectance spectra (1386, 1356, 1327, and 1296 cm(-1)). The [Mn(2)](2+) SMM and [Ni(dmit)(2)](n-) units aggregate independently to form hybrid frames. Electronic conductivity measurements revealed that 1 behaved as a semiconductor (ρ(rt) = 2.1 × 10(-1) Ω·cm(-1), E(a) = 97 meV) at ambient pressure and as an insulator at 1.7 GPa (ρ(1.7GPa) = 4.5 Ω·cm(-1), E(a) = 76 meV). Magnetic measurements indicated that the [Mn(2)](2+) units in 1 behaved as S(T) = 4 SMMs at low temperatures.     

碳化镍钼催化剂的制备及其甲烷干气重整活性(英文)

Nickel molybdenum carbide catalysts were prepared and their activities in the CO2 reforming of methane at a low CO2/CH4 reactant ratio were investigated using a microreactor at atmospheric pressure and at 973 K.The effect of the catalyst preparation method and the Ni/Mo ratio on the increase in catalyst life and the promotion of catalytic activity were investigated using N2 adsorption,X-ray diffraction, temperature-programmed carburization,temperature-programmed reaction,and a reforming reaction.The 25Ni75Mo catalyst that was carburized at 813 K exhibited the highest hydrogen formation ability and gave the least carbon deposition.The incomplete carburization of the Mo oxide species in the catalyst that was carburized at a lower temperature gradually gave a more active carburized species.The NiMoOxCy in the catalyst was more active in hydrogen formation during the dry reforming of methane whileβ-Mo2C andη-Mo3C2 were less active.     

Improving background suppression in diffusion-weighted imaging of the abdomen and pelvis using STIR with single-axis diffusion encoding

Bowel contents and peripheral nerves often show high signal intensity at diffusion-weighted imaging (DWI) of the abdomen and pelvis, obscuring or mimicking pathology. This study introduced and compared short tau inversion recovery (STIR) with single-axis DWI to the usual combination of spectral fat suppression (SFS) with trace DWI in the suppression of bowel contents and peripheral nerves. Five volunteers underwent both STIR with single-axis DWI and SFS with trace DWI of the abdomen and pelvis. Images were evaluated by two observers with respect to the suppression of signal of bowel contents and peripheral nerves using four-point grading scales (4=poor suppression; 3=moderate suppression; 2=good suppression; 1=excellent suppression). Mean scores (±S.D.) regarding the suppression of bowel contents were 1.60±0.55 and 1.40±0.89 for STIR with single-axis DWI and 3.40±0.55 and 3.00±1.00 for SFS with trace DWI for observers 1 and 2, respectively. Mean scores regarding the suppression of peripheral nerves were 1.20±0.45 and 1.20±0.45 for STIR with single-axis DWI and 2.40±0.89 and 2.80±0.84 for SFS with trace DWI for observers 1 and 2, respectively. In conclusion, STIR with single-axis DWI is superior to SFS with trace DWI in the suppression of bowel signal and peripheral nerves.     

Seshadri constants on rational surfaces with anticanonical pencils

We study a Seshadri constant at a general point on a rational surface whose anticanonical linear system contains a pencil. First, we describe a Seshadri constant of an ample line bundle on such a rational surface explicitly by the numerical data of the ample line bundle. Second, we classify log del Pezzo surfaces which are special in terms of the Seshadri constants of the anticanonical divisors when the anticanonical degree is between 4 and 9.     

Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands,meso‐ or rac‐Bis[(diphenylphosphinomethyl)phenylphosphino]methane

A series of tetragold(I) complexes supported by tetraphosphine ligands, meso‐ and rac‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (meso‐ and rac‐dpmppm) were synthesized and characterized to show that the tetranuclear Au^I alignment varies depending on syn‐ and anti‐arrangements of the two dpmppm ligands with respect to the metal chain. The structures of syn‐[Au₄(meso‐dpmppm)₂X]X′₃ (X=Cl; X′=Cl ( 4 a ), PF₆ ( 4 b ), BF₄ ( 4 c )) and syn‐[Au₄(meso‐dpmppm)₂]X₄ (X=PF₆ ( 4 d ), BF₄ ( 4 e ), TfO ( 4 f ); TfO=triflate) involved a bent tetragold(I) core with a counter anion X incorporated into the bent pocket. Complexes anti‐[Au₄(meso‐dpmppm)₂]X₄ (X=PF₆ ( 5 d ), BF₄ ( 5 e ), TfO ( 5 f )) contain a linearly ordered Au₄ string and complexes syn‐[Au₄(rac‐dpmppm)₂X₂]X′₂ (X=Cl, X′=Cl ( 6 a ), PF₆ ( 6 b ), BF₄ ( 6 c )) and syn‐[Au₄(rac‐dpmppm)₂]X₄ (X=PF₆ ( 6 d ), BF₄ ( 6 e ), TfO ( 6 f )) consist of a zigzag tetragold(I) chain supported by the two syn‐arranged rac‐dpmppm ligands. Complexes 4 d–f , 5 d–f , and 6 d–f with non‐coordinative large anions are strongly luminescent in the solid state (λ_max=475–515 nm, Φ=0.67–0.85) and in acetonitrile (λ_max=491–520 nm, Φ=0.33–0.97); the emission was assigned to phosphorescence from ³[d_σ*σ*σ*p_σσσ] excited state of the Au₄ centers on the basis of DFT calculations as well as the long lifetime (a few μs). The emission energy is predominantly determined by the HOMO and LUMO characters of the Au₄ centers, which depend on the bent ( 4 ), linear ( 5 ), and zigzag ( 6 ) alignments. The strong emissions in acetonitrile were quenched by chloride anions through simultaneous dynamic and static quenching processes, in which static binding of chloride ions to the Au₄ excited species should be the most effective. The present study demonstrates that the structures of linear tetranuclear gold(I) chains can be modified by utilizing the stereoisomeric tetraphosphines, meso‐ and rac‐dpmppm, which may lead to fine tuning of the strongly luminescent properties intrinsic to the Au^I₄ cluster centers.     

Strongly luminescent palladium(0) and platinum(0) diphosphine complexes

The synthesis, structure, and photoluminescence of palladium(0) and platinum(0) complexes containing biarydiphosphines, biphep (biphep = 2,2'-bis(diphenylphosphino)-1,1'-biphenyl) and binap (binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) have been studied. X-ray structure analysis of [Pt(biphep)(2)] revealed the distorted-tetrahedral geometry of the complex. The photophysical properties of the three complexes [Pd(biphep)(2)], [Pt(biphep)(2)], and [Pd(binap)(2)] were investigated and compared with that of the previously reported [Pt(binap)(2)] complex. The [Pd(biphep)(2)] complex shows the strongest luminescence with a high quantum yield (38%) and a long lifetime (3.2 micros) in a toluene solution at room temperature. The luminescence should be due to metal-to-ligand charge transfer excited states. At room temperature, radiative rate constants of the four complexes show similar values. The difference in the luminescent properties should reflect the different nonradiative rate constants of the complexes. The temperature-dependence of the luminescence spectra and lifetime of the complexes were also discussed.     

Luminescence from 3,4,9,10-perylenetetracarboxylic dianhydride on Ag(111) surface excited by tunneling electrons in scanning tunneling microscopy

The electronic excitations induced with tunneling electrons into adlayers of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on Ag(111) have been investigated by in situ fluorescence spectroscopy in scanning tunneling microscopy (STM). A minute area of the surface is excited by an electron tunneling process in STM. Fluorescence spectra strongly depend on the coverage of PTCDA on Ag(111). The adsorption of the first PTCDA layer quenches the intrinsic surface plasmon originated from the clean Ag(111). When the second layer is formed, fluorescence spectra are dominated by the signals from PTCDA, which are interpreted as the radiative decay from the manifold of first singlet excited state (S(1)) of adsorbed PTCDA. The fluorescence of PTCDA is independent of the bias polarity. In addition, the fluorescence excitation spectrum agrees with that by optical excitation. Both results indicate that S(1) is directly excited by the inelastic impact scattering of electrons tunneling within the PTCDA adlayer.     

Size control of giant unilamellar vesicles prepared from inverted emulsion droplets

The production of giant lipid vesicles with controlled size and structure will be an important technology in the design of quantitative biological assays in cell-mimetic microcompartments. For establishing size control of giant vesicles, we investigated the vesicle formation process, in which inverted emulsion droplets are transformed into giant unilamellar vesicles (GUVs) when they pass through an oil/water interface. The relationship between the size of the template emulsion and the converted GUVs was studied using inverted emulsion droplets with a narrow size distribution, which were prepared by microfluidics. We successfully found an appropriate centrifugal acceleration condition to obtain GUVs that had a desired size and narrow-enough size distribution with an improved yield so that emulsion droplets can become the template for GUVs.     

Photocurrent generation from hierarchical zinc-substituted hemoprotein assemblies immobilized on a gold electrode

All connected: a protein-immobilized electrode comprising hierarchical assemblies of photoactive cytochrome b(562) reconstituted with zinc protoporphyrin IX exhibits remarkably enhanced photocurrent generation relative to an electrode bearing a single zinc-substituted hemoprotein layer. The protein oligomers, which bear a covalently linked protoporphyrin group, assemble by a supramolecular heme/heme pocket interaction.