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51.
Interactions of three types of tetraalkylammonium cations (tetrapropyltetrabutyl-and tri-isoamylbutyl- ammonium) with perchlorate and tetraphenylborate anions were studied by the conductivity method in 2-butanone from –45°C to 25°C. Conductance data obtained for diluted solutions (5×10–5 – 2×10–3 mol-dm–3) were used to calculate the limiting molar conductivities and associationconstants. The conductance equation of Fuoss-Hsia including the Chen term and the chemical model assumption were applied. Limiting ion conductivities were calculated assuming equal limiting conductivities of the i-Am3BuN+ and BPh
4
–
ions at all temperatures. Gibbs energies and entropies of ion pair formation, calculated from the dependence of association constants on temperature, are presented including the contributions due to short-range forces. 相似文献
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(Z)-Ethyl-3-perfluoroalkyl-3-magnesiated crotonates were prepared from (Z)-ethyl-3-perfluoroalkyl-3-iodo enoates by iodine-magnesium exchange reaction with isopropylmagnesium bromide in THF at -78 degrees C. These new reagents reacted with a range of electrophiles, leading to polyfunctional products bearing a perfluoroalkyl group. 相似文献
54.
Fuxiang Ji Feng Wang Libor Kobera Sabina Abbrent Jiri Brus Weihua Ning Feng Gao 《Chemical science》2021,12(5):1730
Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs2AgInCl6 as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs2AgIn1−xFexCl6 (x = 0–1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe3+ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe3+ replaces diamagnetic In3+ in the Cs2AgInCl6 lattice with the formation of [FeCl6]3−·[AgCl6]5− domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices.Through Fe3+-alloying, the bandgap of benchmark double perovskite Cs2AgInCl6 can be tuned from 2.8 eV to 1.6 eV. The atomic-level structure of Cs2AgIn1−xFexCl6 was revealed by solid-state nuclear magnetic resonance (ssNMR). 相似文献
55.
Stereoselectivity of reductive amination of (R)-1-hydroxy-1-phenylpropan-2-one by methylamine was studied. From the four isomers possible, only two are produced by this
reaction. These are marked as (−)-(1R,2S)-ephedrine (desired product) and (+)-(1S,2R)-ephedrine. The reaction stereoselectivity depends both on the type of the catalyst and reaction conditions. The most suitable
type is the supported platinum. However, this catalyst rapidly deactivates. With a decreasing activity of Pt catalyst, the
stereoselectivity decreases. It is also decreased during the production of the second liquid phase (water) in the reaction
mixture. 相似文献
56.
Inês Nunes Nuno Mesquita Sandra Cabo Verde Maria João Trigo Armando Ferreira Maria Manuela Carolino António Portugal Maria Luísa Botelho 《Radiation Physics and Chemistry》2012,81(12):1943-1946
Parchments are important documents that give testimony for History; therefore these materials should be respected and preserved. Considering incremental biodeterioration problems that have to be faced daily, the Archive of the University of Coimbra (AUC) is involved in different scientific projects in order to evaluate and determine new methods for document decontamination and preservation.The aim of this study was to evaluate gamma radiation effects on the colour and texture of the AUC parchment documents. The assessment of these effects was used to estimate the maximum gamma radiation dose (Dmax) that could guarantee parchment documents′ decontamination treatment, without significant alteration of their physical properties. Parchment samples were exposed to gamma radiation doses ranging from 10 to 30 kGy. The texture and colour of samples were assessed before and after the irradiation procedure, using a texture analyser and an electronic colorimeter. Hardness and springiness were determined based on texture spectra. Lightness (L?), Chroma (C), greenness vs. redness (a*) and yellowness vs. blueness (b*) values were obtained from colorimetric measures. Results indicate no significant effects of gamma radiation on the texture and colour of parchment for the studied doses. 相似文献
57.
New Experimental Insight into the Nature of Metal−Metal Bonds in Digallium Compounds: J Coupling between Quadrupolar Nuclei 下载免费PDF全文
Dr. Libor Kobera Scott A. Southern Dr. Gyandshwar Kumar Rao Prof. Dr. Darrin S. Richeson Prof. Dr. David L. Bryce 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9565-9573
Multiple bonding between atoms is of ongoing fundamental and applied interest. Here, we report a multinuclear (1H, 13C, and 71Ga) solid‐state magnetic resonance spectroscopic study of digallium compounds which have been proposed, albeit somewhat controversially, to contain single, double, and triple Ga?Ga bonds. Of particular relevance to the nature of these bonds, we have carried out two‐dimensional 71Ga J/D‐resolved NMR experiments which provide a direct measurement of J(71Ga,71Ga) spin–spin coupling constants across the gallium?gallium bonds. When placed in the context of clear‐cut experimental data for analogous singly, doubly, and triply bonded carbon spin pairs or boron spin pairs, the 71Ga NMR data clearly support the notion of a different bonding paradigm in the gallium systems. Our findings are consistent with an increasing role across the purported gallane–gallene–gallyne series for classical and/or slipped π‐type bonding orbitals. 相似文献
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The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases. 相似文献