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41.
M Mitsumi T Murase H Kishida T Yoshinari Y Ozawa K Toriumi T Sonoyama H Kitagawa T Mitani 《Journal of the American Chemical Society》2001,123(45):11179-11192
A new one-dimensional (1-D) halogen-bridged mixed-valence diplatinum(II,III) compound, Pt(2)(EtCS(2))(4)I (3), has been successfully synthesized from [Pt(2)(EtCS(2))(4)] (1) and [Pt(2)(EtCS(2))(4)I(2)] (2). These three compounds have been examined using UV-visible-near-IR, IR, polarized Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray crystal structure analyses (except for 1). Compound 3 was further characterized through electrical transport measurements, determination of the temperature dependence of lattice parameters, X-ray diffuse scattering, and SQUID magnetometry. 3 crystallizes in the monoclinic space group C2/c and exhibits a crystal structure consisting of neutral 1-D chains with a repeating -Pt-Pt-I- unit lying on the crystallographic 2-fold axis parallel to the b axis. The Pt-Pt distance at 293 K is 2.684 (1) A in the dinuclear unit, while the Pt-I distances are essentially equal (2.982 (1) and 2.978 (1) A). 3 shows relatively high electrical conductivity (5-30 S cm(-1)) at room temperature and undergoes a metal-semiconductor transition at T(M-S) = 205 K. The XPS spectrum in the metallic state reveals a Pt(2+) and Pt(3+) mixed-valence state on the time scale of XPS spectroscopy ( approximately 10(-17) s). In accordance with the metal-semiconductor transition, anomalies are observed in the temperature dependence of the crystal structure, lattice parameters, X-ray diffuse scattering, and polarized Raman spectra near T(M-S). In variable-temperature crystal structure analyses, a sudden and drastic increase in the Pt-I distance near the transition temperature is observed. Furthermore, a steep increase in U(22) of iodine atoms in the 1-D chain direction has been observed. The lattice parameters exhibit significant temperature dependence with drastic change in slope at about 205-240 K. This was especially evident in the unit cell parameter b (1-D chain direction) as it was found to lengthen rapidly with increasing temperature. X-ray diffraction photographs taken utilizing the fixed-film and fixed-crystal method for the metallic state revealed the presence of diffuse scattering with line shapes parallel to the a* axis indexed as (-, n + 0.5, l) (n; integer). Diffuse scattering with k = n + 0.5 is considered to originate from the 2-fold periodical ordering corresponding to -Pt(2+)-Pt(2+)-I-Pt(3+)-Pt(3+)-I- or -Pt(2+)-Pt(3+)-I-Pt(3+)-Pt(2+)-I- in an extremely short time scale. Diffuse lines corresponding to 2-D ordering progressively decrease in intensity below 252 K and are converted to the diffuse planes corresponding to 1-D ordering near T(M-S). Furthermore, diffuse planes condensed into superlattice reflections below T(M-S). Polarized Raman spectra show temperature dependence through a drastic low-energy shift of the Pt-I stretching mode and also through broadening of bands above T(M-S). 相似文献
42.
Progress in theory and experiment on the early stage of decomposition of alloys is reviewed. In the first half of this paper, theoretical treatments on decomposition of alloys by spinodal and nucleation mechanism and also continuum theories and the discrete lattice theories are comparatively reviewed. In the latter half of this paper, experimental results on Al-Zn, Ni-Al, Cu-Co and Al-Ag alloys are discussed. 相似文献
43.
44.
Yoshito Mitani Judith Velina Lara-Manzano Aaron Rodriguez-Lopez 《Accreditation and quality assurance》2008,13(7):421-426
According to the experience of the successful implementation of proficiency tests (PT) by using the certified reference value
as the assigned value, a new scheme of evaluation is presented by suggesting the use of the uncertainty associated with the
certified value. The technical performance of laboratories is evaluated by the parameter quadratic mean error (QME), which
is the square root of the sum of the square of the bias and that of the standard deviation of the laboratory. This parameter
is considered as the estimate of the measurement uncertainty of the laboratory and is compared to the uncertainty (U) associated with the certified value provided by an NMI. Considering that the calibration and measurement capability, known
as the CMC, is recognized among NMIs, the ratio QME/U enables us to compare the PT relative to the CMC of an NMI, and, consequently, to any other comparison results based on the
CMC of signatories of the mutual recognition arrangement (MRA) of the International Committee of Weights and Measure (CIPM).
Presented at BERM-11, October 2007, Tsukuba, Japan. 相似文献
45.
Shirakawa E Itoh K Higashino T Hayashi T 《Journal of the American Chemical Society》2010,132(44):15537-15539
Sodium tert-butoxide mediates the coupling of aryl halides with benzene derivatives without the aid of transition metal catalysts but with a catalytic 1,10-phenanthroline derivative. 相似文献
46.
Upon visible-light irradiation, reductive carboxylation of alkyl halides takes place by using a SmI2/Sm mixed system under atmospheric CO2 to afford the corresponding carboxylic acids in good to excellent yields. 相似文献
47.
Mizoshita N Yamanaka K Shimada T Tani T Inagaki S 《Chemical communications (Cambridge, England)》2010,46(48):9235-9237
Polycondensation of 9-mesityl-10-methylacridinium-bridged organosilane in the presence of a nonionic surfactant yielded a mesostructured organosilica solid with a functional framework that exhibited long-lived photoinduced charge separation. 相似文献
48.
Yoshiteru Sakata Hiroshi Imahori Ken-Ichi Sugiura 《Journal of inclusion phenomena and macrocyclic chemistry》2001,41(1-4):31-36
Guidelines for the design of molecules with a long lifetime of the charge-separated state and for the formation of a self-assembled monolayer were studied by preparing various model compounds linking donor and acceptor with chemical bonds. Based on the obtained results we designed and prepared the SAMs of C60-(porphyrin)-(ferrocene)-(CH2)11SH on a gold surface and observed a photocurrent with high efficiency (25% quantum yield). In addition, a well-defined, rigid-sheet-structured oligoporphyrin with 21 porphyrin chromophores was prepared as a model for antenna chlorophylls. 相似文献
49.
Ken-Ichi Maruyama 《Topology》2007,46(3):319-341
We study nilpotent subgroups of automorphism groups in the category of groups and the homotopy category of spaces. We establish localization and completion theorems for nilpotent groups of automorphisms of nilpotent groups. We then apply these algebraic theorems to prove analogous results for certain groups of self-homotopy equivalences of spaces. 相似文献
50.
Jean-Francois Bisson Hideki Yagi Takakimi Yanagitani Alexander Kaminskii Yuri N. Barabanenkov Ken-Ichi Ueda 《Optical Review》2007,14(1):1-13
Grain boundaries play a key role in determining several key properties of polycrystalline laser ceramics. Heat transfer measurements
at low temperature constitute a good tool to probe grain boundaries. We review the results of heat transfer measurements in
polycrystalline Y3Al5O12 garnets as well as Y2O3 and Lu2O3 sesquioxide materials obtained by self-energy-driven sintering of nano-particles. The average phonon mean free path in Y3Al5O12 was found to be significantly larger than the average grain size and to scale with temperature as T
−2 at low temperature. Existing models describing the interaction between phonons and grain boundaries are reviewed. Correct
temperature dependence of the mean free path and order of magnitude of scattering rates were found by assuming the existence
of a grain boundary layer having acoustic properties different from those of the bulk. A different temperature dependence
of phonon mean free path was found for the sesquioxides and was ascribed to the stronger elastic anisotropy of these materials.
The thermal resistance associated to the grain boundaries of laser ceramics was found to be lower than in other dense polycrystalline
ceramic materials reported in the literature. 相似文献