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951.
Tomohito Morosaki Tsubasa Suzuki Wei‐Wei Wang Shigeru Nagase Takayoshi Fujii 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(36):9723-9725
Electronic effects on the central carbon atom of carbone, generated by the replacement of the SIV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph2E, E=S or Se), were investigated. The carbones Ph2E→C←SPh2(NMe) [E=S( 1 ) or Se( 2 )] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2 , which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2 > 1 >CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four‐electron donor. 相似文献
952.
Katsuya Oji Asako Igashira‐Kamiyama Nobuto Yoshinari Takumi Konno 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(7):2023-2027
A novel AuICoIII coordination system that is derived from the newly prepared [Co(D ‐nmp)2]− ( 1 −; D ‐nmp=N‐methyl‐D ‐penicillaminate) and a gold(I) precursor AuI is reported. Complex 1 − acts as a sulfur‐donating metallaligand and reacts with the gold(I) precursor to give [Au2Co2(D ‐nmp)4] ( 2 ), which has an eight‐membered AuI2CoIII2 metallaring. Treatment of 2 with [Au2(dppe)2]2+ (dppe=1,2‐bis(diphenylphosphino)ethane) leads to the formation of [Au4Co2(dppe)2(D ‐nmp)4]2+ ( 3 2+), which consists of an 18‐membered AuI4CoIII2 metallaring that accommodates a tetrahedral anion (BF4−, ClO4−, ReO4−). In solution, the metallaring structure of 3 2+ is readily interconvertible with the nine‐membered AuI2CoIII metallaring structure of [Au2Co(dppe)(D ‐nmp)2]+ ( 4 +); this process depends on external factors, such as solvent, concentration, and nature of the counteranion. These results reveal the lability of the Au S and Au P bonds, which is essential for metallaring expansion and contraction. 相似文献
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Shao‐Bo Mi 《Surface and interface analysis : SIA》2014,46(2):102-105
Structural properties of YBa2Cu3O7‐δ/PrBa2Cu3O7‐δ heterointerfaces have been investigated by aberration‐corrected electron microscopy. Experimental evidence shows that c‐axis‐oriented YBa2Cu3O7‐δ/PrBa2Cu3O7‐δ heterostructures with atomically sharp interface epitaxially grow on SrTiO3(001) substrates. In terms of the contrast analysis, no apparent interdiffusion between YBa2Cu3O7‐δ and PrBa2Cu3O7‐δ occurs at the interface. In addition, stand‐off misfit dislocations and planar faults appear within PrBa2Cu3O7‐δ layer near the interface. Both misfit dislocations and interfacial dislocations resulting from the termination of planar faults contribute to misfit relaxation at the YBa2Cu3O7‐δ/PrBa2Cu3O7‐δ interface. The defect configuration of planar faults and stand‐off misfit dislocations is explored. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
958.
Martin Schmid Hans‐Peter Steinrück J. Michael Gottfried 《Surface and interface analysis : SIA》2014,46(8):505-511
Asymmetric peak profiles for the application in spectroscopy can be obtained in a simple way by substituting the usually constant full width at half maximum parameter in Pseudo‐Voigt functions with an energy‐dependent expression, for instance of sigmoidal shape. While this approach has been successfully applied to vibrational spectra, we find that the resulting curves are less suitable for least‐squares fits of X‐ray photoelectron spectroscopy (XPS) data. However, if one additionally allows a variable displacement of the sigmoidal step relative to the peak, excellent fitting results can be obtained. We demonstrate the applicability of our extended approach on several inherently asymmetric XPS lines, i.e. the C 1s signal of graphite and C2H2/Pd(100), the 3d5/2–3d3/2 doublet of palladium, and the 4f7/2–4f5/2 doublet of platinum. Comparison of the corresponding fit results with the results obtained by the application of more elaborate, theory‐based line profiles (Doniach‐?unji? and Mahan functions) shows that the modified Pseudo‐Voigt function gives practically identical results in terms of peak shape and area, while requiring much less computational effort since no convolution procedures are required for its calculation. Thus, this function is most suitable for application in one of the following situations: (i) the peak shape of a given signal is known but cannot be calculated with ease, and (ii) the theoretical peak shape is not (yet) known, however, one wants to perform a first quantitative screening of the data at issue. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
959.
Electroless Ni–P and Ni–P–TiCN composite coatings have been deposited successfully on Al substrates. Scanning electron microscopy (SEM) and energy dispersive X‐ray (EDX) techniques were applied to study the surface morphology and the chemical composition of the deposited films. Moreover, X‐ray diffraction (XRD) proved that Ni–P and Ni–P–TiCN deposits have amorphous structures. The properties of Ni–P–TiCN/Al composite films such as hardness, corrosion resistance and electrocatalytic activity were examined and compared with that of Ni–P/Al film. The results of hardness measurements reveal that the presence of TiCN particles with Ni–P matrix improves its hardness. Additionally, the performance against corrosion was examined using Tafel lines and electrochemical impedance spectroscopy techniques in both of 0.6 M NaCl and a mixture of 0.5 M H2SO4 with 2 ppm HF solutions. The results indicate that the incorporation of high dispersed TiCN particles into Ni–P matrix led to a positive shift of the corrosion potential and an increase in the corrosion resistance for all aluminum substrates after their coating with Ni–P–TiCN. In addition, Ni–P–TiCN/Al electrodes showed a higher electrochemical catalytic activity and stability toward methanol oxidation in 0.5 M NaOH solution compared with that of Ni–P/Al. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
960.
Wenjuan Cheng Lu‐Tao Weng Yongjie Li Arthur Lau Chak Chan Chi‐Ming Chan 《Surface and interface analysis : SIA》2014,46(7):480-488
Size‐segregated particles were collected with a ten‐stage micro‐orifice uniform deposit impactor from a busy walkway in a downtown area of Hong Kong. The surface chemical compositions of aerosol samples from each stage were analyzed using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) operated in the static mode. The ToF‐SIMS spectra of particles from stage 2 (5.6–10 µm), stage 6 (0.56–1 µm), and stage 10 (0.056–0.1 µm) were compared, and the positive ion spectra from stage 2 to stage 10 were analyzed with principal component analysis (PCA). Both spectral analysis and PCA results show that the coarse‐mode particles were associated with inorganic ions, while the fine particles were associated with organic ions. PCA results further show that the particle surface compositions were size dependent. Particles from the same mode exhibited more similar surface features. Particles from stage 2 (5.6–10 µm), stage 6 (0.56–1 µm), and stage 10 (0.056–0.1 µm) were further selected as representatives of the three modes, and the chemical compositions of these modes of particles were examined using ToF‐SIMS imaging and depth profiling. The results reveal a non‐uniform chemical distribution from the outer to the inner layer of the particles. The coarse‐mode particles were shown to contain inorganic salts beneath the organics surface. The accumulation‐mode particles contained sulfate, nitrate, ammonium salts, and silicate in the regions below a thick surface layer of organic species. The nucleation‐mode particles consisted mainly of soot particles with a surface coated with sulfate, hydrocarbons, and, possibly, fullerenic carbon. The study demonstrated the capability of ToF‐SIMS depth profiling and imaging in characterizing both the surface and the region beneath the surface of aerosol particles. It also revealed the complex heterogeneity of chemical composition in size and depth distributions of atmospheric particles. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献