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51.
A larger quantity of a β-keto ester that is 1.5–1.7 equiv more than the base (t-BuOK, NaH) was found to be essential in securing sufficient yields of the products in the palladium-catalyzed allylic substitution of the monoacetate of 4-cyclopentene-1,3-diol with β-keto esters. This requirement also works well for substitutions with the TBS ether of the monoacetate and the monoacetate of 2-cyclohexene-1,4-diol. As an application, the coronafacic acid ethyl ester was synthesized as an optically active form. 相似文献
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Prof. Hisahiro Sasabe Prof. Yuki Kato Dr. Yuichiro Watanabe Tatsuya Ohsawa Dr. Naoya Aizawa Prof. Wataru Fujiwara Dr. Yong-Jin Pu Prof. Hiroshi Katagiri Prof. Junji Kido 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16294-16300
Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C−H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τP) of 1.1 s and a phosphorescence quantum yield (ΦP) of 1.2 %, whereas the bromine-substituted derivative exhibits τP of 0.15 s with a ΦP of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP. 相似文献
55.
The present status of our understanding of the diffusion of hydrogen in metals, both experimental and theoretical, is reviewed. Discussions are focused on the mechanism of diffusion of hydrogen isotopes H, D and T in f.c.c. and b.c.c. metals; the positive muon (μ +) is referred to where appropriate. An up-to-date compilation of diffusion data as a function of temperature and isotope mass has been made, and a clear distinction in general diffusion behaviour in f.c.c. and b.c.c. metals is noted. Subsequently, the results obtained from the Gorsky effect, nuclear magnetic resonance and quasi-elastic neutron scattering that provide information on elementary jump processes are discussed. A conceptual framework of the quantum diffusion of light interstitials in metals is given, including the recent Kondo theory that emphasizes the crucial importance of particle-conduction electron interactions in the diffusion process, especially at low temperatures. It is shown with the help of recent estimates of the tunneling matrix element that the overall feature of diffusion of hydrogen isotopes in b.c.c. metals as well as μ + in f.c.c. metals can be explained consistently within the frame presented here. Finally, recent advances in the diffusion studies on hydrogen in b.c.c. metals are described. They include a re-analysis of quench-recovery experiments that manifested nearly athermal diffusion of H, D and T in Ta at low temperatures, and an enormous enhancement of the diffusivity under stress (superdiffusion) observed for H and D in V. 相似文献
56.
Dr. Yoji Horii Dr. Keiichi Katoh Dr. Kunihisa Sugimoto Dr. Ryo Nakanishi Dr. Brian K. Breedlove Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3098-3104
In the research field of single-molecule magnets (SMMs), lanthanoid–lanthanoid interactions, so-called f–f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f–f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII-CdII-phthalocyaninato sextuple-decker complex (Dy2Cd3) reveals that the intramolecular Dy−Dy length in Dy2Cd3 is more than 13 Å, which is longer than the intermolecular Dy−Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole–dipole interactions are observed in Dy2Cd3. From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2Cd3 is partially suppressed owing to the existence of very weak Dy−Dy interactions. Our results show that even very weak Dy−Dy interactions act as a dipolar bias, suppressing QTM. 相似文献
57.
Homo‐double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines
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Wataru Makiguchi Shinzo Kobayashi Keisuke Furukawa Hiroki Iida Yoshio Furusho Eiji Yashima 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):990-999
An optically active, m‐terphenyl‐based π‐conjugated polymer bearing carboxy groups was synthesized by the copolymerization of the diethynyl monomer bearing a carboxy group with (S,S)‐2,5‐bis(2‐methylbutoxy)‐1,4‐dibromobenzene using Sonogashira reaction. The copolymer showed a weak circular dichroism (CD) in the main‐chain chromophore region due to a homo‐double helix formation with an excess helical handedness biased by the chiral alkoxy substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double helix was also induced in the polymer in the presence of nonracemic amines. The effect of the achiral and chiral amines on the homo‐double helix formation was investigated by comparing the CD spectra of the polymer to those of its model dimer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 990–999 相似文献
58.
Jie Wang Denan Li Honggui Yang Shufan Yao Prof. Qianqian Zhu Prof. Masahiro Sadakane Prof. Yanshuo Li Prof. Wataru Ueda Prof. Zhenxin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(41):e202200618
Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. 31P NMR spectroscopy shows that reduction of MoVI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na+ is used as the adsorbent, which effectively separates C2 hydrocarbon mixtures. 相似文献
59.
Polymerization of tetrafluoroethylene was carried out in bulk at low temperatures by initiation with γ-rays from a 60 Co source. It was found that a remarkable postpolymerization takes place even in the liquid phase. Kinetical analysis has been made of the in-source and postpolymerizations. An activation energy of 2.7 kcal/mole was obtained for the in-source polymerization and 10.3 kcal/mole for the postpolymerization. The long lifetime of polymer radicals in the liquid phase at -78°C seems to be due to the slow recombination rate of the polymer radicals, based on the rodlike shape of the polymer radicals. 相似文献
60.
Masakatsu Sugimoto Kazuhiko Fujiwara Ryuhei Wakita Toshiyuki Kida Araki Masuyama Yohji Nakatsuji 《Supramolecular chemistry》2013,25(2-3):145-151
Abstract Acyclic multidentate ligands consisting of an oligooxyethylene chain (di-, tri-, tetra-, and penta-) and two terminal rigid quinaldate end groups were newly prepared and their complexation properties with alkali metal cations were estimated by the solvent extraction method to indicate a better affinity for K+. Among them, the tetraethylene glycol derivative showed the highest K+ binding on about the same level as 18-crown-6. Their conformations in solution and in the solid state were examined by using 1H- and 13C-NMR spectroscopy and X-ray crystal analyses, respectively. The better binding of K+ in comparison with the corresponding glymes or analogues having the same donor sites was reasonably explained by considering the effective co-ordination of the carbonyl oxygen of the ester groups and the parallel π-stacking interaction between two quinaldate surfaces. 相似文献