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41.
Roman Tkachov Lukas Stepien Aljoscha Roch Hartmut Komber Felix Hennersdorf Jan J. Weigand Ingmar Bauer Anton Kiriy Christoph Leyens 《Tetrahedron》2017,73(16):2250-2254
Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[Kx(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K2[3]). Heating of K2[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K4[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K2[4]), the product of the decarbonylation of K2[3]. Preliminary experiments reveal that the involvement of K2[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications. 相似文献
42.
Sarah Crotty Felix H. Schacher Ulrich S. Schubert 《Journal of polymer science. Part A, Polymer chemistry》2012,50(23):4958-4965
We report the synthesis and characterization of well‐defined homo‐ and diblock copolymers containing poly(furfuryl glycidyl ether) (PFGE) via living anionic ring‐opening polymerization using different initiators. The obtained materials were characterized by SEC, MALDI‐TOF MS, and 1H NMR spectroscopy and molar masses of up to 9400 g/mol were obtained for PFGE homopolymers. If the amphiphilic diblock copolymer PEG‐block‐PFGE was dissolved in water, micelles with a PFGE core and a PEG corona were formed. Hereby, the hydrophobic PFGE core domains were used for the incorporation of a suitable bismaleimide and heating to 60 °C induced the crosslinking of the micellar core via Diels‐Alder chemistry. This process was further shown to be reversible. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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Dr. Steffen Thies Hanno Sell Dr. Claudia Bornholdt Christian Schütt Dr. Felix Köhler Prof. Dr. Felix Tuczek Prof. Dr. Rainer Herges 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16358-16368
The bistability of spin states (e.g., spin crossover) in bulk materials is well investigated and understood. We recently extended spin‐state switching to isolated molecules at room temperature (light‐driven coordination‐induced spin‐state switching, or LD‐CISSS). Whereas bistability and hysteresis in conventional spin‐crossover materials are caused by cooperative effects in the crystal lattice, spin switching in LD‐CISSS is achieved by reversibly changing the coordination number of a metal complex by means of a photochromic ligand that binds in one configuration but dissociates in the other form. We present mathematical proof that the maximum efficiency in property switching by such a photodissociable ligand (PDL) is only dependent on the ratio of the association constants of both configurations. Rational design by using DFT calculations was applied to develop a photoswitchable ligand with a high switching efficiency. The starting point was a nickel–porphyrin as the transition‐metal complex and 3‐phenylazopyridine as the photodissociable ligand. Calculations and experiments were performed in two iterative steps to find a substitution pattern at the phenylazopyridine ligand that provided optimum performance. Following this strategy, we synthesized an improved photodissociable ligand that binds to the Ni–porphyrin with an association constant that is 5.36 times higher in its trans form than in the cis form. The switching efficiency between the diamagnetic and paramagnetic state is efficient as well (72 % paramagnetic Ni–porphyrin after irradiation at 365 nm, 32 % paramagnetic species after irradiation at 440 nm). Potential applications arise from the fact that the LD‐CISSS approach for the first time allows reversible switching of the magnetic susceptibility of a homogeneous solution. Photoswitchable contrast agents for magnetic resonance imaging and light‐controlled magnetic levitation are conceivable applications. 相似文献
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Melanie Schmidlehner Felix Faschinger Lorenz Michael Reith Martin Ertl Wolfgang Schoefberger 《应用有机金属化学》2013,27(7):395-405
In this study, novel water‐soluble corrole amino acid conjugates were synthesized and characterized. The coupling reaction of A2B‐ and A3‐corroles with glycine ethyl ester and taurine under strong basic conditions proved to be successful and yielded di‐ and trifunctionalized corrole amino acid conjugates in good yields. The subsequent metalation of the corrole/amino acid conjugates broadens the scope for applications considerably. As examples, we herein show the catalytic activity of the Mn(III) A3‐corrole towards O2 evolution. First we employed tert‐butyl hydroperoxide (t‐BuOOH) as oxidant to obtain the Mn(V)oxo species and tetrabutyl ammonium hydroxide (TBAH) as hydroxide donor agent. Furthermore, the binding properties of the non‐metalated and the Mn(III) A3‐corrole/amino sulfonic acid conjugates and transport of proteins were investigated and the conjugates exhibited binding to human serum albumin (HSA). Finally, a novel Ga(III) A3‐corrole/amino sulfonic acid derivative was synthesized and we briefly describe the photophysical properties of this compound. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Analyse von Protease‐Inhibitor‐Interaktionen unter Nutzung evolvierbarer tricyclischer Microviridine
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