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21.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
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Remarkable stability of the oxirane function is displayed over a number of synthetic operations in a novel synthesis of the antitumor compound epothilone B (see scheme). The cis-epoxide, generated very early by dihydroxylation of an (E)-olefin, was resistant to more than ten synthetic steps under a wide variety of reaction conditions. TBS=tert-butyldimethylsilyl. 相似文献
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Kortunov P Vasenkov S Kärger J Fé Elía M Perez M Stöcker M Papadopoulos GK Theodorou D Drescher B McElhiney G Bernauer B Krystl V Kocirik M Zikanova A Jirglova H Berger C Gläser R Weitkamp J Hansen EW 《Magnetic resonance imaging》2005,23(2):233-237
Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts. 相似文献
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Prumper G Zimmermann B Langer B Viefhaus J Hentges R Cherepkov NA Schmidtke B Drescher M Heinzmann U Becker U Kleinpoppen H 《Physical review letters》2000,85(24):5074-5077
The linear magnetic dichroism in the angular distribution of Tl 5d and 6p photoelectrons and their dynamical spin polarization have been measured between hnu = 30 and 50 eV. In contrast to the Xe 5p photoionization at the 4d threshold, our results show that above the Tl 5d threshold strong interchannel coupling effects induce a sudden increase in the asymptotic phase difference of the s and d waves for the Tl 6p ionization. This shows that the valence excitation is different for resonant (Xe 4d) and nonresonant (Tl 5d) excitation from subvalence shells. 相似文献
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Several choices of scaling are investigated for a coupled system of parabolic partial differential equations in a two‐phase medium at the microscopic scale. This system may be regarded as modelling a reaction–diffusion problem, the Stokes problem of single‐phase flow of a slightly compressible fluid or as a heat conduction problem (with or without interfacial resistance), for example. It is shown that, starting with the same problem on the microscopic scale, different choices of scaling of the diffusion coefficients (resp. permeability or conductivity) and the interfacial‐exchange coefficient lead to different types of macroscopic systems of equations. The characterization of the limit problems in terms of the scaling parameters constitutes a modelling tool because it allows to determine the right type of limit problem. New macroscopic models, not previously dealt with, arise and, for some scalings, classical macroscopic models are recovered. Using the method of two‐scale convergence, a unified approach yielding rigorous proofs is given covering a very broad class of different scalings. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
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