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71.
A catalytic pinacol coupling using water as a solvent was performed by a catalytic amount of vanadium(III) chloride and metallic Al as a co-reductant. A combination forms a binary catalytic system, being in sharp contrast to the reaction in organic solvent, which requires a chlorosilane as an additive. Various aromatic aldehydes underwent the reductive coupling to give the corresponding 1,2-diols in moderate to good yields. 相似文献
72.
Zhao Y Higashihara T Sugiyama K Hirao A 《Journal of the American Chemical Society》2005,127(41):14158-14159
Novel 3-arm ABC, 4-arm ABCD, and 5-arm ABCDE asymmetric star polymers comprising the conductive polyacetylene precursor, poly(4-methylphenyl vinyl sulfoxide) (PMePVSO), and other segments, such as polystyrene, poly(alpha-methylstyrene), poly(4-methoxystyrene), poly(4-trimethylsilylstyrene), and poly(4-methylstyrene), were synthesized by the methodology based on living anionic polymerization using DPE-functionalized polymers. This methodology involves the addition reaction of a DPE-functionalized polymer to a living anionic polymer followed by the living anionic polymerization of MePVSO initiated from the in situ formed polymer anion with two, three, or four polymer segments. The resultant asymmetric star polymers possessed predetermined molecular weights, narrow molecular weight distributions (Mw/Mn < 1.03), and desired compositions as confirmed by SEC, 1H NMR, SLS, and elemental analysis. After thermal treatment, the PMePVSO segment in the star polymer could be completely converted into a conductive polyacetylene segment, evident from TGA and elemental analysis. These asymmetric star polymers are expected to exhibit interesting solution properties and unique microphase-separated morphological suprastructures with potential applications in nanoscopic conductive materials. Moreover, this methodology can afford the target asymmetric star polymers with arm segments varying in a wide range and enables the synthesis of more complex macromolecular architectures. 相似文献
73.
Kenzo Ohkita Hideo Kurosawa Toshikazu Hirao Isao Ikeda 《Journal of organometallic chemistry》1994,470(1-2):189-190
Relative stability in coordination of substituted styrene derivatives to [Ru(η-C5H5)(dtpe)]+ (dtpe = 1,2-bis(di-p-tolylphosphino)-ethane) was determined by NMR spectroscopy to reveal unusually weak substituent dependency of the stability. 相似文献
74.
A method for analyzing the A(1u)/A(2u) contents of metalloporphyrin pi-cation radicals is developed and applied to a series of unsubstituted planar metalloporphines (MPs) (M=Cr, Mn, Fe, Co, Ni, Cu, and Zn). The structures and electronic properties of the MPs and their cation radicals were calculated by density functional theory (DFT) and subsequently analyzed. It was found that the MPs with small core sizes have a tendency to form A(1u)-type radicals, while the MPs with large core size have a preference for an A(2u)-type. Neither of these pure-state species, however, is stable under the D(4)(h) symmetry, and both radical cation types are subject to pseudo-Jahn-Teller (pJT) distortion. The pJT distortion leads to structures with lower symmetry and states that have mixed character with respect to the A(1u) and A(2u) components. The degree of mixing could be estimated by employing orbital projection technique or a complementary spin density decomposition. Both techniques produce very similar results, pointing out that the frontier orbital, which becomes empty upon electron removal, plays a critical role in determining electronic properties. 相似文献
75.
Palladium nanoparticles (PdNPs) were successfully attached and grown on an indium tin oxide (ITO) surface using a seed-mediated growth method, i.e., via a simple two-step immersion of the ITO substrate into the seed and growth solutions. After the growth treatment for 24 h, PdNPs grew up to 60-80 nm, exhibiting crystal-like appearances and accompanying the formation of short rodlike nanocrystals as a minor product. Thus prepared PdNPs tend to stick each other, so that the dense gathering of PdNPs was observed on the ITO surfaces. Due to the dense attachment, the PdNPs directly attached to the ITO (PdNP/ITO) electrode had a significantly lowered charge-transfer resistivity compared with that of a bare ITO, and the redox reaction of [Fe(CN)6]3-/[Fe(CN)6]4- was observed as reversible in 0.1 M phosphate buffer solution. The electrocatalytic property of PdNPs was confirmed for the reduction of oxygen. In addition, some typical responses were observed in 0.5 M H2SO4 with the PdNP/ITO electrode, reflecting both the characteristics of NPs and the thin layer in nanoscale. The present preparation method of PdNP-attached surfaces would be promising for catalytic applications as well as electrochemical uses. 相似文献
76.
A complete set of elastic constants C ij and piezoelectric coefficients e ij of a La3Ga5SiO14 (langasite) single crystal was determined from 5.5 to 275.5?K by resonant ultrasound spectroscopy. Unlike a conventional crystal, the elastic constants C ij of the langasite crystal showed three types of temperature dependence: (i) monotonic elastic stiffening upon cooling (C 44 and C 14); (ii) monotonic elastic softening (C 66); and (iii) a stiffening-to-softening transition below 150?K (C 11, C 12, C 13 and C 33). In addition, a strong correlation between C 66 and the piezoelectric coefficient e 11 was confirmed. Group theoretical lattice dynamics analysis revealed that the novel phenomena of elastic softening and strong correlation are explained on the basis of two types of optical mode internal displacements which have the totally symmetric A 1 and doubly degenerated E symmetries in the point group D 3. 相似文献
77.
Recently, we proposed a simple yet efficient method for the computation of a long-range corrected (LC) hybrid scheme [LC-DFT(2Gau)], which uses a modified two-Gaussian attenuating operator instead of the error function for the long-range HF exchange integral. This method dramatically reduced the computational time while maintaining the improved features of the LC density functional theory (DFT). Here, we combined an LC hybrid scheme using a two-Gaussian attenuating operator with one-parameter progressive correlation functional and Becke88 exchange functional with varying range-separation parameter values [LC-BOP(2Gau) with various μ values of 0.16, 0.2, 0.25, 0.3, 0.35, 0.4, and 0.42] and demonstrated that LC-BOP(2Gau) reproduces well the thermochemical and frontier orbital energies of LC-BOP. Additionally, we revised the scaling factors of the Gaussian multipole screening scheme for LC-DFT(2Gau) to correspond to the angular momentum of orbitals, which decreased the energy deviations from the energy with the no-screening scheme. © 2018 Wiley Periodicals, Inc. 相似文献
78.
Mamoru Furuta Takahiro Hiramatsu Tokiyoshi Matsuda Chaoyang Li Hiroshi Furuta Takashi Hirao 《Journal of Non》2008,354(17):1926-1931
Zinc oxide (ZnO) film was deposited on a glass substrate by rf magnetron sputtering with O2/Ar as working gases. Structural properties of the films were characterized by XRD. Average crystallite size in the films was strongly dependent on both the gas flow ratio of O2/Ar and rf-power at a constant deposition pressure. During the deposition, energetic species in the plasma were in situ monitored using optical emission spectroscopy. An inverse correlation was observed between the average crystallite size and the emission intensity ratio of IO∗/IAr. Bombardment of atomic oxygen to the growing surface played an important role in determining the average crystallite size in the films. The average crystallite size could be controlled by the emission intensity ratio of IO∗/IAr. 相似文献
79.
Norimasa Umesaki
Naoto Hirosaki
Kazuyuki Hirao
《Journal of Non》1992,150(1-3):120-125Computer simulation, using the molecular dynamics (MD) technique, has been carried out on amorphous silicon nitride (a-Si3N4) with simple Busing-type potentials. From the MD simulation, the following points have been deduced. (1) The average Si---N bond length obtained from MD results is rSi---N=1.74 Å, and its coordination number, NSi---N, is 3.95. The bond angles around a Si and a N atom, N---Si---N and Si---N---Si, are found to be 109.8° ± 12.36° and 127.08° ± 16.63°, respectively. The N---Si---N value obtained is in very good agreement with the tetrahedral bond angle (= 109.47°). Hence, the short-range structural arrangement of a-Si3N4 comprises tetrahedral SiN4 units. The MD results presented in this study also indicate that there exist only a small number of defects such as dangling bonds. (2) These MD results are in good agreement with the reported X-ray and neutron data. The a-Si3N4 structure can be reproduced by the MD simulation given in this study. 相似文献
80.
Kouzou Matsumoto Dr. Toru Tanaka Sota Kugo Takuya Inagaki Yoshikazu Hirao Dr. Hiroyuki Kurata Dr. Takeshi Kawase Dr. Takashi Kubo Dr. 《化学:亚洲杂志》2008,3(12):2024-2032
Tetrakis(bithienyl)methane and tetrakis(terthienyl)methane have been synthesized from tetrakis(2‐thienyl)methane by use of Suzuki–Miyaura coupling as a key reaction. Their trimethylsilyl (TMS) derivatives are also synthesized. X‐ray analysis reveals that each oligothiophene moiety tends to adopt anti‐conformations and show relatively small torsion angles between the adjacent thiophene rings. While the longest absorption maxima of these tetrakis(oligothienyl)methanes exhibit only a slight bathochromic shift compared to the corresponding linear oligothiophene derivative, tetrakis(bithienyl)methane and its TMS derivative exhibit an appreciable red‐shift in their fluorescence spectra. The intramolecular interaction between thienyl groups of tetrakis(2‐thienyl)methane is supported by DFT calculation. 相似文献