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Dr. Jan Keuter Maria Dimitrova Dr. Oliver Janka Dr. Alexander Hepp Priv. Doz. Dr. Raphael J. F. Berger Dr. Felicitas Lips 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(45):e202201473
The silanide [Si4{N(SiMe3)Dipp}3]− ( 1 ) transforms into the anionic siliconoid cluster [Si7{N(SiMe3)Dipp}3]− ( 2 ) with four unsubstituted silicon atoms as a contact ion pair with [K([18]crown-6)] in C6D6 at room temperature within five weeks. Anion 2 was investigated by natural population analysis and visualization of intrinsic atomic orbitals. Magnetically induced current-density calculations of 2 revealed two distinct strong diatropic vortices that sum up in one direction and create a strongly shielded apical silicon atom in 2 . 相似文献
14.
Koranit Shlosman Ran Y. Suckeveriene Jasmine Rosen‐Kligvasser Roza Tchoudakov Evgeni Zelikman Raphael Semiat Moshe Narkis 《先进技术聚合物》2014,25(12):1484-1491
This paper summarizes a study of controlled migration of an antifog (AF) additive; sorbitan monooleate (SMO), from linear low density polyethylene (LLDPE) films containing a compatibilizer, LLDPE grafted maleic anhydride (LLDPE‐g‐MA). LLDPE/LLDPE‐g‐MA/SMO blends were prepared by melt compounding. Bulk and surface properties of compression molded LLDPE films containing SMO and LLDPE‐g‐MA were characterized using Fourier transform infrared spectroscopy and contact angle measurements. Thermal properties were investigated using a thermal gravimetric analyzer. Diffusion coefficient (D) was calculated, and AF properties were characterized using a “hot fog” test. Compression molded films were characterized for their morphology using high‐resolution scanning electron microscopy, and rheological properties were measured using a parallel‐plate rotational rheometer. It was found that the LLDPE/LLDPE‐g‐MA/SMO systems are characterized by a slower SMO migration rate, a lower diffusion coefficient, and lower contact angle values compared with LLDPE/SMO blends. These results are well correlated with results of a hot fog test. Morphological studies revealed a very fine dispersion of SMO in the LLDPE films, when 3 phr LLDPE‐g‐MA was combined with 1 phr SMO. Thermal analysis results show that the incorporation of 3 phr LLDPE‐g‐MA and 1 phr SMO significantly increases the decomposition temperature of the blend at T > 400°C. At high shear rates, the LLDPE blends show that the AF and the compatibilizer have a lubrication effect on LLDPE. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
15.
HOMO Stabilisation in π‐Extended Dibenzotetrathiafulvalene Derivatives for Their Application in Organic Field‐Effect Transistors 下载免费PDF全文
Dr. Yan Geng Dr. Raphael Pfattner Antonio Campos Prof. Wei Wang Dr. Olivier Jeannin Dr. Jürg Hauser Dr. Joaquim Puigdollers Prof. Stefan T. Bromley Prof. Silvio Decurtins Prof. Jaume Veciana Prof. Concepció Rovira Dr. Marta Mas‐Torrent Dr. Shi‐Xia Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16672-16679
Three new organic semiconductors, in which either two methoxy units are directly linked to a dibenzotetrathiafulvalene (DB‐TTF) central core and a 2,1,3‐chalcogendiazole is fused on the one side, or four methoxy groups are linked to the DB‐TTF, have been synthesised as active materials for organic field‐effect transistors (OFETs). Their electrochemical behaviour, electronic absorption and fluorescence emission as well as photoinduced intramolecular charge transfer were studied. The electron‐withdrawing 2,1,3‐chalcogendiazole unit significantly affects the electronic properties of these semiconductors, lowering both the HOMO and LUMO energy levels and hence increasing the stability of the semiconducting material. The solution‐processed single‐crystal transistors exhibit high performance with a hole mobility up to 0.04 cm2 V?1 s?1 as well as good ambient stability. 相似文献
16.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes 下载免费PDF全文
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
17.
Denise T. B. De Salvi Hernane S. Barud Agnieszka Pawlicka Ritamara I. Mattos Ellen Raphael Younés Messaddeq Sidney J. L. Ribeiro 《Cellulose (London, England)》2014,21(3):1975-1985
New bacterial cellulose (BC)–triethanolamine (TEA) ion-conducting membranes have been prepared and characterized. The samples were obtained by soaking BC membranes in triethanolamine aqueous solutions and drying. The scanning electron microscopy pictures revealed that the incorporation of TEA in BC membranes covers the cellulose microfibrils. Raman spectra exhibited BC and TEA characteristic group frequencies and thermal analysis evidenced an influence of TEA content on the sample thermal stability. The ion-conductivity as a function of the temperature showed an Arrhenius behavior increasing from 1.8 × 10?5 S/cm at room temperature to 7.0 × 10?4 S/cm at 80 °C for the BC–TEA 1 M sample. 相似文献
18.
Lisa A. Bischoff Jarno Riefer Raphael Wirthensohn Tobias Bischof Rüdiger Bertermann Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13615-13620
Salts of the tetrakis(pentafluoroethyl)aluminate anion [Al(C2F5)4]− were obtained from AlCl3 and LiC2F5. They were isolated with different counter-cations and characterized by NMR and vibrational spectroscopy and mass spectrometry. Degradation of the [Al(C2F5)4]− ion was found to proceed via 1,2-fluorine shifts and stepwise loss of CF(CF3) under formation of [(C2F5)4−nAlFn]− (n=1–4) as assessed by NMR spectroscopy and mass spectrometry and supported by results of DFT calculations. In addition, the [(C2F5)AlF3]− ion was structurally characterized. 相似文献
19.
Raphael Bigler Kyle A. Mack Jeff Shen Paolo Tosatti Chong Han Stephan Bachmann Haiming Zhang Michelangelo Scalone Andreas Pfaltz Scott E. Denmark Stefan Hildbrand Francis Gosselin 《Angewandte Chemie (International ed. in English)》2020,59(7):2844-2849
Asymmetric hydrogenation has evolved as one of the most powerful tools to construct stereocenters. However, the asymmetric hydrogenation of unfunctionalized tetrasubstituted acyclic olefins remains the pinnacle of asymmetric synthesis and an unsolved challenge. We report herein the discovery of an iridium catalyst for the first, generally applicable, highly enantio‐ and diastereoselective hydrogenation of such olefins and the mechanistic insights of the reaction. The power of this chemistry is demonstrated by the successful hydrogenation of a wide variety of electronically and sterically diverse olefins in excellent yield and high enantio‐ and diastereoselectivity. 相似文献
20.
Felix Nußbaumer Raphael Plangger Manuel Roeck Christoph Kreutz 《Angewandte Chemie (International ed. in English)》2020,59(39):17062-17069
We present the access to [5‐19F, 5‐13C]‐uridine and ‐cytidine phosphoramidites for the production of site‐specifically modified RNAs up to 65 nucleotides (nts). The amidites were used to introduce [5‐19F, 5‐13C]‐pyrimidine labels into five RNAs—the 30 nt human immunodeficiency virus trans activation response (HIV TAR) 2 RNA, the 61 nt human hepatitis B virus ? (hHBV ?) RNA, the 49 nt SAM VI riboswitch aptamer domain from B. angulatum, the 29 nt apical stem loop of the pre‐microRNA (miRNA) 21 and the 59 nt full length pre‐miRNA 21. The main stimulus to introduce the aromatic 19F–13C‐spin topology into RNA comes from a work of Boeszoermenyi et al., in which the dipole‐dipole interaction and the chemical shift anisotropy relaxation mechanisms cancel each other leading to advantageous TROSY properties shown for aromatic protein sidechains. This aromatic 13C–19F labeling scheme is now transferred to RNA. We provide a protocol for the resonance assignment by solid phase synthesis based on diluted [5‐19F, 5‐13C]/[5‐19F] pyrimidine labeling. For the 61 nt hHBV ? we find a beneficial 19F–13C TROSY enhancement, which should be even more pronounced in larger RNAs and will facilitate the NMR studies of larger RNAs. The [19F, 13C]‐labeling of the SAM VI aptamer domain and the pre‐miRNA 21 further opens the possibility to use the biorthogonal stable isotope reporter nuclei in in vivo NMR to observe ligand binding and microRNA processing in a biological relevant setting. 相似文献