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Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
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Jun Fujii Giancarlo Panaccione Giorgio Rossi Giancarlo Trimarchi 《Surface science》2006,600(18):3884-3887
Bulk carbon impurities segregate at the Fe(1 0 0) surface and, upon thermal annealing, can form metastable surface phases with local and long range order and peculiar electronic properties. We present a surface science study of C-segregated Fe(1 0 0) with scanning tunneling microscopy, angle resolved photoemission, and ab initio calculations of the surface structure and electron states. In particular the c(3√2 × √2) structure, observed for 0.67 atomic layers of C segregated at the iron surface, is found to be due to self-organized carbon stripes made of zig-zag chains. The strong hybridization between C and Fe was observed in ARPES spectra. 相似文献
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XPS measurement revealed that the original state of TiO2 was changed to Ti2O3 and TiO by ion bombardment. TiO2 decreased and Ti2O3 increased at the initial stage. TiO increased at a later stage than Ti2O3. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO2 to Ti2O3 and from Ti2O3 to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO2 to Ti2O3 is about ten times larger than that from Ti2O3 to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment. 相似文献
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The potential of the internal rotation of the methyl group was determined for o-, m-, and p-fluorotoluene cations by pulsed field ionization spectroscopy. The potential of the internal rotational motion was also surveyed for other toluene derivative cations. It was found that the barrier height generally increases by ionization. The increase in the barrier height has been discussed in connection with the reduction of the internal rotational constant B by ionization. The geometrical distortion of the methyl group during the internal rotation has been suggested. 相似文献
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Masayuki Kuzuya Akihiro Noguchi Hideki Ito Shin-Ichi Kondo Nahoko Noda 《Journal of polymer science. Part A, Polymer chemistry》1991,29(1):1-7
Plasma-induced polystyrene radicals were first studied by electron spin resonance (ESR). The room temperature ESR spectrum was compared with those obtained by γ-irradiation, UV-irradiation, and mechanical fracture. It was found that even less than a few seconds of plasma-irradiation gave rise to a large amount of polystyrene radicals and the ESR spectrum consisted of two types of spectra, a triplet and a single broad line. The spectral feature of the triplet was nearly identical with that of γ-irradiated polystyrene. Thus, it was assigned to the structure of a cyclohexadienyl-type radical formed by a nearly random addition of a hydrogen atom to the aromatic ring. The single broad line, thought to be an outline of multicomponent spectrum, was assigned to an immobilized dangling-bond sites at the plasma-induced crosslinked portion of the polystyrene surface. 相似文献
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