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41.
Prof. Tomoaki Tanase Miho Tanaka Mami Hamada Yuka Morita Dr. Kanako Nakamae Prof. Yasuyuki Ura Prof. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8219-8224
A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4−nPtn(μ-rac-dpmppan)2(XylNC)2](PF6)2 (XylNC=xylyl isocyanide; n=0: Pd4 ( 1 ), 1: PtPd3 ( 2 ), 2: PtPd2Pt ( 3 ), 2: Pt2Pd2 ( 4 ), 3: Pt2PdPt ( 5 )), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31P{1H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1 – 5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain. 相似文献
42.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
43.
Yayoi Yoshioka 《Colloid and polymer science》2013,291(7):1641-1648
Nano-sized aromatic polyamide particles with trifluoromethyl groups were prepared via a precipitation polymerization method from 4,4′-diphenyldicarbonyl chloride and 2,2-bis(4-aminophenyl)hexafluoropropane in a dioxane solution containing pyridine. The average diameter of the particles decreased from ca. 500 to 150 nm as the pyridine content increased. The particles were spherical with narrow size distributions. Also, the inherent viscosity and yield of the particles decreased gradually as the pyridine content increased. For all the particles, the degrees of crystallinity were low, and the thermal decomposition temperatures were above 457 °C. The addition of pyridine significantly influenced not only the polymerization but also the affinity between the product and the reaction solution, resulting in a difference in the diameters and characteristic features of the particles. Furthermore, these characteristic features were found to be determined predominantly during precipitation from the reaction solution. Meanwhile, trifluoromethyl groups in the particles had significant influence on the morphology and characteristic features of the particles. 相似文献
44.
Shin-ichi Kondo Kimihiro Endo Jun Iioka Keisuke Sato Yuka Matsuta 《Tetrahedron letters》2017,58(43):4115-4118
We have successfully prepared 5-(2-phenylethynyl)isophathalilc acid as a signaling unit and the corresponding derivatives for an anion receptor 2 and a barbiturate receptor 4. Receptor 2 showed characteristic UV–vis changes and dramatic fluorescence quenching upon the addition of anions and receptor 4 showed UV–vis and an OFF-ON fluorescence changes upon the addition of dibutylbarbituric acid based on the diphenylethyne moiety. 相似文献
45.
Hiroyuki Nishide Naoki Yoshioka Yukoh Saitoh Ritsuko Gotoh Takeshi Miyakawa Eishun Tsuchida 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):775-786
Abstract m- and p Bis(diphenylene)propenylphenylacetylene (m-, p-8) were synthesized and polymerized with WCI6, MoCl5, and Rh catalyst, yielding solvent-soluble poly(phenylacetylene)s bearing a π-conjugated bis(di-phenylene)propenyl groups (m-, p-7a). The polymers gave their polyanion derivatives, which were electrolytically and chemically oxidized to yield the corresponding polyradicals (m-, p-7b). The polyradicals were chemically very stable due to the resonance stabilization of an unpaired electron whose spin concentration could be increased up to ca. 2 × 1023 spins per molar monomer unit. ESR spectroscopy suggested an antiferro-magnetic interaction between unpaired electrons. 相似文献
46.
Complexation of some lanthanide ions with poly(methacrylic acid) and its copolymers was studied by potentiometric titration. Poly [methacrylic acid-co-oligo(ethylene oxide)methacrylate] and poly(methacrylic acid-co-acrylamide) formed tris-carboxylate coordinate lanthanide complexes with large overall complexation constants, while poly-(methacrylic acid)s and copolymer with higher content of the methacrylic acid residue formed bis-coordinate ones. It was concluded that the comonomer residues in the copolymer chains decreased the steric hindrance for the complexation and/or acted as co-coordinating groups of the carboxylic group to lanthanide ions. Very large positive and favorable entropy changes were observed for the complexation with poly(methacrylic acid) and its copolymers. This contribution of thermodynamic parameters to the complexation was contrary to that for the analogous monomeric methacrylic acid complex and is assumed to be induced by dehydration of the polymers through the lanthanide ion complexation. 相似文献
47.
An efficient synthesis of new hydroazulene derivatives, 13 and 14, potential intermediates for the syntheses of the the title terpenes, via intramolecular [2 + 2] photocycloaddition is described in the context of the total synthesis of (±)-daucene. 相似文献
48.
Shintaro Wakamatsu Yuka Takahashi Dr. Hidetsugu Tabata Dr. Tetsuta Oshitari Norihiko Tani Prof. Dr. Isao Azumaya Dr. Yukiteru Katsumoto Dr. Takeyuki Tanaka Dr. Shinzo Hosoi Prof. Dr. Hideaki Natsugari Prof. Dr. Hideyo Takahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(22):7056-7063
The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations. 相似文献
49.
Dr. Takuya Nakashima Kyohei Yamamoto Yuka Kimura Prof. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16972-16980
Herein, we designed chiral photoresponsive tetra(2‐phenylthiazole)s, which induce a diastereoselective 6π‐electrocyclization reaction in a helically folded structure to freeze the conformational interconversions. The folding conformation with one helical turn of tetra(2‐phenylthiazole)s was supported by multiple intramolecular noncovalent interactions including vicinal S???N interheteroatom interactions and CH–π and π–π stacking interactions between nonadjacent units, as found in X‐ray crystal structures as well as quantum chemical calculations. The introduction of a chiral group at both ends of tetra(2‐phenylthiazole) dictates the preferential folding into a one‐handed helix conformation by the simultaneous operation of S???O and multiple CH–π interactions that involve the chiral end groups. Since the tetra(2‐phenylthiazole)s possess two equivalent photoreactive 6π‐electron systems and the folded conformation is suitable for photoinduced electrocyclization reaction, they undergo a photocyclization reaction in a stereoselective manner to memorize the chirality of the helix in a resulting diastereomeric closed form. 相似文献
50.
Nicolas Zigon Manabu Hoshino Shota Yoshioka Yasuhide Inokuma Makoto Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(31):9161-9165
Crystal structures of α‐humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio‐ and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold‐related compounds were successfully determined for samples on a 5–50 μg scale. 相似文献