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91.
Aleksei S. Pronin Spartak S. Yarovoy Yakov M. Gayfulin Aleksey A. Ryadun Konstantin A. Brylev Denis G. Samsonenko Ilia V. Eltsov Yuri V. Mironov 《Molecules (Basel, Switzerland)》2020,25(24)
Compounds based on new cyanide cluster anions [{Mo6I8}(CN)6]2–, trans-[{Mo6I8}(CN)4(MeO)2]2– and trans-[{W6I8}(CN)2(MeO)4]2− were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo6I8}4+ and {W6I8}4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo6I8} and {W6I8} cluster cores can be achieved by coordination of cyanide ligands. 相似文献
92.
Haojie Zhang Dirk J. Hagen Xiaopeng Li Andreas Graff Frank Heyroth Bodo Fuhrmann Ilya Kostanovskiy Stefan L. Schweizer Francesco Caddeo A. Wouter Maijenburg Stuart Parkin Ralf B. Wehrspohn 《Angewandte Chemie (International ed. in English)》2020,59(39):17172-17176
Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co‐P films were deposited by using PH3 plasma as the phosphorus source and an extra H2 plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self‐limited layer‐by‐layer growth, and the deposited Co‐P films were highly pure and smooth. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures. 相似文献
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94.
Mami Miyairi Tsuyoshi Taniguchi Tatsuya Nishimura Katsuhiro Maeda 《Angewandte Chemie (International ed. in English)》2020,59(35):14772-14780
An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism. 相似文献
95.
Ranjit Bag Sourav Kar Suvam Saha Suman Gomosta Beesam Raghavendra Thierry Roisnel Sundargopal Ghosh 《化学:亚洲杂志》2020,15(6):780-786
Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe2(CO)9] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl4] (Cp*=η5‐C5Me5) and [LiBH4?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ3‐BH)2H2{Cp*W(CO)2}2{Fe(CO)2}] ( 1 ) and bis‐borylene, [(μ3‐BH)2{Cp*W(CO)2}2{Fe(CO)3}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru3(CO)12]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ3‐BH)2{WCp*(CO)2}2{Ru(CO)3}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co2(CO)8] with nido‐[(RhCp*)2(B3H7)], which afforded triply‐bridging bis‐borylene species [(μ3‐BH)2(RhCp*)2Co2(CO)4(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; 1H, 11B, 13C NMR spectroscopy; IR spectroscopy and mass spectrometry. 相似文献
96.
为研究高硬度钢板抗不同着角钨球的侵彻性能及破坏模式,通过弹道枪进行了?8 mm、?11 mm钨合金球形破片以0°、20°、40°着角撞击厚度为6 mm、8 mm的高硬度钢板试验,得到了极限贯穿速度v50;分析了钨球轴向径向变形及靶板失效模式与撞击速度的关系,发现高硬度钢板失效模式主要为压缩开坑破坏和沿厚度方向剪切破坏。采用有限元方法对试验进行了模拟,验证了数值模型及参数的合理性,并运用数值模拟方法研究了撞击着角对靶板吸能模式影响,结合试验数据,修正已有极限贯穿速度计算公式。结果表明:随侵彻着角增大,极限贯穿速度提高,且着角越大,极限贯穿速度增长越快;随着角增大,靶板吸能模式逐渐由压缩开坑向剪切冲塞过渡,且着角大于50°时,剪切冲塞耗能将超过压缩开坑耗能;修正后极限贯穿速度计算公式适用范围更广、精度更高,具有较好工程应用价值。 相似文献
97.
B. Goldstein 《辐射效应与固体损伤》2013,168(3-4):229-237
Single crystal silicon, both with and without oxygen, has been diffused with lithium to concentrations ~1017/cm2, irradiated with 1 to 1.5 MeV electrons, and the ensuing defects studies by EPR measurements. The presence of oxygen strongly affects the properties of these defects. Measurements have indicated the presence of two new defects which involve Li-one in O-containing material and one in O-free material. The defects are observed in their electron-filled state, and indicate a net electron spinof ½. The defect spectra disappear (with time) at room temperature, and can be explained by the formation of other Li-involved defects which lie deeper in the energy bandgap and are not visible by EPR. Electron irradiation at 40 °K followed by annealing at higher temperatures show that both EPR defects described above begin to form at about 200 °K and begin to decrease at about 275 °K-just as does the 250 °K reverse annealing observed generally for n-type Si. Based on these data, and the work of others, it is suggested that both defects form as a result of the motion of Si interstitials which produce a (Li-O-interstitial) complex in O-containing Si, and a (Li-interstitial) complex in O-free Si. 相似文献
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