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101.
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Prof. Piotr Bałczewski Dr. Emilia Kowalska Dr. Ewa Różycka-Sokołowska Dr. Joanna Skalik Dr. Krzysztof Owsianik Dr. Marek Koprowski Dr. Bernard Marciniak Dr. Dariusz Guziejewski Prof. Witold Ciesielski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14148-14161
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen. 相似文献
103.
Peter T. Smith Younghoon Kim Dr. Bahiru Punja Benke Prof. Kimoon Kim Prof. Christopher J. Chang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4932-4937
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications. 相似文献
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Mathematical Notes - An algorithm is presented which determines in a finite number of steps whether an initial finite binary automaton is spherically transitive. Since the class of deterministic... 相似文献
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Tereshchenko E. D. Cherniakov S. M. Yurik R. Yu. Rietveld M. T. Häggström I. 《Radiophysics and Quantum Electronics》2020,62(10):667-676
Radiophysics and Quantum Electronics - We present the results of comparing the total electron content measurements based on GLONASS satellite signals and the EISCAT UHF incoherent scatter radar... 相似文献
109.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes
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María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
110.