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排序方式: 共有598条查询结果,搜索用时 15 毫秒
1.
Oliver Back Dr. Christoph Förster Prof. Dr. Thomas Basché Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6542-6552
2-Iminopyrroles [HtBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBuL), aggregate to dimers, [M(tBuL)(NCR)]2 (M=Li, R=CH3, CH(CH3)CNH2), or polymers, [M(tBuL)]n (M=Na, K). In solution (solv=CH3CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBuL)(solv)m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission. 相似文献
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Winald R. Kitzmann Prof. Dr. Katja Heinze 《Angewandte Chemie (International ed. in English)》2023,62(15):e202213207
Transition metal complexes with photoactive charge-transfer excited states are pervasive throughout the literature. In particular, [Ru(bpy)3]2+ (bpy=2,2′-bipyridine), with its metal-to-ligand charge-transfer emission, has been established as a key complex. Meanwhile, interest in so-called spin-flip metal-centered states has risen dramatically after the molecular ruby [Cr(ddpd)2]3+ (ddpd=N,N′-dimethyl-N,N′-dipyridin-2-yl-pyridine-2,6-diamine) led to design principles to access strong, long-lived emission from photostable chromium(III) complexes. This Review contrasts the properties of emissive charge-transfer and spin-flip states by using [Ru(bpy)3]2+ and [Cr(ddpd)2]3+ as prototypical examples. We discuss the relevant excited states, the tunability of their energy and lifetimes, and their response to external stimuli. Finally, we identify strengths and weaknesses of charge-transfer and spin-flip states in applications such as photocatalysis and circularly polarized luminescence. 相似文献
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From Infinite Chains according to 1∞[Zr(S2O7)4/2] in Zr(S2O7)2 to the unprecedented [Zr(S2O7)4]4– Anion in Ag4[Zr(S2O7)4] 下载免费PDF全文
The reaction of ZrCl4 with oleum (65 % SO3) in the presence of Ag2SO4 at 250 °C yielded colorless single crystals of Zr(S2O7)2 [orthorhombic, Pccn, Z = 4, a = 709.08(6) pm, b = 1442.2(2) pm, c = 942.23(9) pm, V = 963.5(2) × 106 pm3]. Zr(S2O7)2 shows Zr4+ ions in an eightfold distorted square antiprismatic coordination of oxygen atoms belonging to four chelating disulfate units. Each S2O72– ion is connected to a further Zr4+ ion leading to chains according to 1∞[Zr(S2O7)4/2]. The same reaction at a temperature of 150 °C resulted in the formation of Ag4[Zr(S2O7)4] [monoclinic, C2/c, Z = 4, a = 1829.35(9) pm, b = 704.37(3) pm, c = 1999.1(1) pm, β = 117.844(2)°, V = 2277.6(2) × 106 pm3]. Ag4[Zr(S2O7)4] exhibits the unprecedented [Zr(S2O7)4]4– anion, in which the central Zr4+ cation is coordinated by four chelating disulfate units. Thus, in Ag4[Zr(S2O7)4] the 1∞[[Zr(S2O7)4/2] chains observed in Zr(S2O7)2 are formally cut into pieces by the implementation of Ag+ ions. 相似文献
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Objective and Methods: We describe the insurance behaviour of subjects (n=271) who had previously taken a predictive genetic test for hereditary non-polyposis colorectal cancer (HNPCC); 31% of them were mutation positive, indicating a high risk of cancer. One year after testing, subjects were sent a questionnaire including questions about their present life and health insurance before participation in the study, and their actual and planned purchase of the insurance policies during the testing programme which compromised a pre-test counseling session, a period for reflection, the testing, and a test disclosure session. Results: Thirty percent reported that they already had a life insurance and 14% a health insurance before participating in the study. The mutation-positive subjects possessed a health insurance significantly more often than the mutation-negative individuals (21 vs. 11%, p=0.02) and similar trend was observed for life insurance (36 vs. 28%, p=0.12). Life and health insurance policies purchased just before testing was reported by 3 and 2% of the subjects, respectively. Life and health insurance policies purchased after testing were reported by 3 and <1% respectively, and planned purchase by 3 and 2%, respectively. No statistically significant differences were found between the groups defined by mutation status in reports of life or health insurance behaviour during or after the programme. Conclusion: According to self-reported data, the mutation-positive subjects did not differ from the others in the purchase of life or health insurance policies. However, the mutation-positive individuals reported that they possessed health insurance policies before entering the study more often than their counterparts. 相似文献
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Katja Fröhlich Evgeny Legotin Frank Bärhold Atanaska Trifonova 《Journal of Solid State Electrochemistry》2017,21(12):3403-3410
The spray roasting process is recently applied for production of catalysts and single metal oxides. In our study, it was adapted for large-scale manufacturing of a more complex mixed oxide system, in particular symmetric lithium nickel manganese cobalt oxide (LiNi1/3Co1/3Mn1/3O2—NMC), which is already used as cathode material in lithium-ion batteries. An additional lithiation step was coupled with the main process in order to obtain the desired layered structure. Thermogravimetric analysis and high-temperature X-ray diffractometry built the basis for determining suitable synthesis temperature regions for the used chloride precursors and the post-treatment step. The optimized process was proven on an industrial pilot line where a setup for minimum production capacity of 12 kg h?1 was possible. The powder obtained directly after roasting had a very striking morphology compared to the final lithiated product. Hollow aggregates (≥250 μm) with overall 10.926 m2 g?1 surface area and a pore diameter of 3.396 nm were observed. Their well-faceted primary particles were converted into nanosized spheres after lithiation, building a few micrometer big high-porous agglomerates. Actual composition was verified by inductively coupled plasma atomic emission spectroscopy analysis, and the crystal structure and corresponding unit cell parameters were identified and confirmed by Rietveld fit of the derived X-ray diffraction pattern. The initial electrochemical measurements show a 149-mAh g?1discharge capacity, as determined from cyclic voltammetry. 相似文献
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