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31.
A novel, cis‐transoidal poly‐(phenylacetylene) bearing a carboxybiphenyl group as the pendant (poly‐ 1 ) was prepared by polymerization of (4′‐ethoxycarbonyl‐4‐biphenylyl)acetylene with a rhodium catalyst followed by hydrolysis of the ester groups. Upon complexation with various chiral amines and amino alcohols in dimethyl sulfoxide (DMSO), the polymer exhibited characteristic induced circular dichroism (ICD) in the UV/Vis region due to the predominantly one‐handed helix formation of the polymer backbone as well as an excess of a single‐handed, axially twisted conformation of the pendant biphenyl group. Poly‐ 1 complexed with (R)‐2‐amino‐1‐propanol showed unique time‐dependent inversion of the macromolecular helicity. Furthermore, the preferred‐handed helical conformation of poly‐ 1 induced by a chiral amine was further “memorized” after the chiral amine was replaced with achiral 2‐aminoethanol or n‐butylamine in DMSO. In sharp contrast to the previously reported memory in poly((4‐carboxyphenyl)acetylene), the present helicity memory of poly‐ 1 was accompanied by memory of the twisted biphenyl chirality in the pendants. Unprecedentedly, the helicity memory of poly‐ 1 with achiral 2‐aminoethanol was found to occur simultaneously with inversion of the axial chirality of the biphenyl groups followed by memory of the inverted biphenyl chirality, thus showing a significant change in the CD spectral pattern. 相似文献
32.
Dr. Tomoyuki Ikai Sayaka Miyoshi Dr. Kosuke Oki Dr. Ranajit Saha Dr. Yuh Hijikata Prof. Eiji Yashima 《Angewandte Chemie (International ed. in English)》2023,62(20):e202301962
Fully π-conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect-free synthesis and resolution of a fully π-conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid-promoted alkyne benzannulations of a rationally designed, random-coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix-inversion barrier, the isolated excess one-handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10−2 and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well-supported by molecular dynamics simulation. 相似文献
33.
Yashima M Enoki M Wakita T Ali R Matsushita Y Izumi F Ishihara T 《Journal of the American Chemical Society》2008,130(9):2762-2763
MEM nuclear density analysis from neutron diffraction data measured in situ at 1015.6 degrees C has indicated the two-dimensional network of curved O2-O3-O2 oxide-ion diffusion paths on the (Pr,La)-O layer in a K2NiF4-type structured oxide-ionic and electronic mixed conductor (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+delta. 相似文献
34.
We report on the oligosaccharide recognition through noncovalent interactions in water based on a unique supramolecular homoduplex-to-heteroduplex transformation of the oligoresorcinol nonamer as a fully artificial receptor. The oligoresorcinol forms a double helix in water, which unravels and entwines upon complexation with specific oligosaccharides with a particular chain length and glucosidic linkage pattern, thus generating the heteroduplex with an excess one-handed helical conformation that can be readily monitored and further quantified by absorption, circular dichroism, and NMR spectroscopies. 相似文献
35.
An optically active helical poly(phenylacetylene) was synthesized by the copolymerization of phenylacetylenes bearing optically active hydroxy or ester groups obtained by the kinetic resolution of a racemic phenylacetylene with lipase; the helix-sense was inverted from one helix to another by the further chemical modification of the hydroxy groups with achiral bulky isocyanates or an acid chloride. 相似文献
36.
Dr. Fenghua Ding Atsunori Doi Dr. Takafumi Ogawa Dr. Hiroki Ubukata Dr. Tong Zhu Dr. Daichi Kato Dr. Cédric Tassel Dr. Itaru Oikawa Dr. Naoki Inui Dr. Satoru Kuze Tsutomu Yamabayashi Dr. Kotaro Fujii Prof. Masatomo Yashima Prof. Xing Ou Dr. Zhijian Wang Prof. Xiaobo Min Prof. Koji Fujita Prof. Hitoshi Takamura Prof. Akihide Kuwabara Tianren Zhang Prof. Kent J. Griffith Prof. Zhang Lin Prof. Liyuan Chai Prof. Hiroshi Kageyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(15):e202401779
The Li3MX6 compounds (M=Sc, Y, In; X=Cl, Br) are known as promising ionic conductors due to their compatibility with typical metal oxide cathode materials. In this study, we have successfully synthesized γ-Li3ScCl6 using high pressure for the first time in this family. Structural analysis revealed that the high-pressure polymorph crystallizes in the polar and chiral space group P63mc with hexagonal close-packing (hcp) of anions, unlike the ambient-pressure α-Li3ScCl6 and its spinel analog with cubic closed packing (ccp) of anions. Investigation of the known Li3MX6 family further revealed that the cation/anion radius ratio, rM/rX, is the factor that determines which anion sublattice is formed and that in γ-Li3ScCl6, the difference in compressibility between Sc and Cl exceeds the ccp rM/rX threshold under pressure, enabling the ccp-to-hcp conversion. Electrochemical tests of γ-Li3ScCl6 demonstrate improved electrochemical reduction stability. These findings open up new avenues and design principles for lithium solid electrolytes, enabling routes for materials exploration and tuning electrochemical stability without compositional changes or the use of coatings. 相似文献
37.
Ikeda M Tanaka Y Hasegawa T Furusho Y Yashima E 《Journal of the American Chemical Society》2006,128(21):6806-6807
We describe the construction of the first double-stranded metallosupramolecular helical polymers. We designed and synthesized a supramolecular duplex comprised of complementary m-terphenyl-based strands bearing a chiral amidine or achiral carboxylic acid together with two pyridine groups at the four ends. Supramolecular polymerization of the duplex with cis-PtPh2(DMSO)2 in 1,1,2,2-tetrachloroethane produced the double-stranded metallosupramolecular polymer with a controlled helicity of which the two complementary metallostrands are intertwined through the amidinium-carboxylate salt bridges. The structures and hydrodynamic dimensions of the metallosupramolecular polymers were characterized by 1H NMR, diffusion-ordered NMR, dynamic light scattering, absorption, and CD measurements. The polymeric structure was also visualized by atomic force microscopy. 相似文献
38.
Kajitani T Okoshi K Sakurai S Kumaki J Yashima E 《Journal of the American Chemical Society》2006,128(3):708-709
We report the unprecedented helix-sense controlled polymerization of enantiomerically pure phenyl isocyanides bearing an l- or d-alanine pendant with a long alkyl chain. The polymerization with an achiral nickel catalyst diastereoselectively proceeds, resulting in either a right- or left-handed helical polymer, whose helix-sense can be controlled by the polymerization solvent and temperature. Both the diastereomeric right- and left-handed helical polymers further self-assemble into lyotropic cholesteric liquid crystals with opposite twist-senses. Consequently, the macromolecular helicity and mesoscopic, supramolecular cholesteric twist can be controlled by the molecular chirality of the pendant of a single enantiomeric phenyl isocyanide through the polymerization under either kinetic or thermodynamic control assisted by hydrogen bonds. High-resolution atomic force microscopy revealed their helical conformations and enabled the determination of the helical sense. 相似文献
39.
K. Ohnaka K. Sagara Y. Maeda K. Ishibashi S. Kimura S. Tanaka T. Fukunaga J. Yasuda T. Yabe K. Yashima Y. Eguchi H. Shimoda T. Sueta S. Kuroita 《Few-Body Systems》2014,55(8-10):725-728
Space Star (SS) anomaly in nd breakup cross section was first reported in 1989 at E n = 13 MeV (Strate et al. in Nucl Phys A 501:51, 1989), but its origin has not been found yet. In order to obtain suggestions for its origin, we made systematic measurements of pd breakup cross section around SS. In SS configuration, three outgoing nucleons form an equilateral triangle and the triangle is perpendicular to the beam axis. Necessity of the equilateral and perpendicular conditions of SS anomaly was investigated by systematic experiments. Also energy dependence of SS anomaly is being studied at energies from E p = 7.5 to 13 MeV. 相似文献
40.
Catalytic activity and aromatic selectivity of n‐butane transformation were studied over various MFI type zeolites. From the data obtained, a reaction mechanism is suggested for different catalyst systems. It is visualized that in gallium doped catalysts, Ga3+ directly takes part both in cracking and dehydrogenation. The [Ga CH3]2+ and [GaH]2+ species formed during cracking and dehydrogenation require protonic sites for regeneration of Ga3+ species. An alternative mechanism was suggested for dehydrogenation and cracking by Ga3+ without the involvement of protonic sites. However a protonic site would be required for aromatization. In case of gallosilicates a one step mechanism is suggested for cracking and dehydrogenation reaction which does not require the presence of protonic sites in the catalyst system. 相似文献