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1.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity
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Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
2.
Heat transfer in a resist-coated silicon wafer using a bake process is theoretically evaluated by modeling the three-dimensional diffusion process, focusing on the controllability of the lithographic performance of chemically amplified resists. Six models of various ambient conditions are used. The proximity gap between the hotplate and the wafer is found to have a dominant influence on the heat transfer process for the whole system. Because the atmosphere near the wafer acts as a thermal diffusion buffer layer, no temperature gradient occurs in the resist, even when it is subjected to convective heat transfer from the resist surface. Experimental results obtained by X-ray lithography confirm the calculation results. 相似文献
3.
Kentaro Suzuya Tomoaki Kamiyama Takemi Yamamura Kiyohito Okamura Kenji Suzuki 《Journal of Non》1992,150(1-3):167-171
A small-angle X-ray scattering (SAXS) study was performed to reveal the nanometer scale hybrid structure of Si---Ti---C---O fibers prepared by the pyrolysis of polytitanocarbosilane. The SAXS profile for Si---Ti---C---O fibers is attributed to two different types of scattering entities: an anisotropic contribution from long filaments with diameters hundreds to thousands of Ångströms and an isotropic contribution from β-SiC fine clusters of about a nanometer in diameter. A drastic degradation in the tensile strength of the fibers is correlated to the characteristic variations in their long-and medium-range structure. 相似文献
4.
Yasushi Arakawa Tomoaki MurakamiFumiko Ozawa Yukimi ArakawaShigeyuki Yoshifuji 《Tetrahedron》2003,59(38):7555-7563
Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO4 oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid. 相似文献
5.
Catalytic asymmetric Mannich-type reactions in water proceeded in high yields and selectivities using a combination of ZnF2 and a chiral diamine that has the methoxy groups on the aromatic rings. In these reactions, either syn- or anti-Mannich adducts were stereospecifically obtained from (E)- or (Z)-silicon enolate, in contrast with most asymmetric Mannich-type reactions. 相似文献
6.
Maekawa K Shiomi D Ise T Sato K Takui T 《The journal of physical chemistry. B》2005,109(19):9299-9304
Spin alignments in heterospin chains are examined from numerical calculations of model spin Hamiltonians. The Hamiltonians of the heterospin chains mimic an open-shell molecular assemblage composed of an organic biradical in a singlet (S = 0) ground state and a doublet (S = 1/2) monoradical, which are coupled by intermolecular ferromagnetic exchange interactions. It is found from numerical calculations of the spin Hamiltonians that the spin value S2 of the ground-state singlet biradical embedded in the exchange-coupled assemblage deviates from zero and contributes to the bulk magnetization. The alternating chain is found to have two kinds of ground spin states, a high- and a low-spin state. All the spins are parallel to each other in the high-spin state, which is characterized by the spin correlation function of (S(i).S(j)) = 0.25. On the other hand, the spin alignment in the low-spin state is found to be dependent on the topology of the intermolecular exchange interactions. The energy preference of the two states depends on the relative amplitude of the exchange interactions in the chain. The intermolecular ferromagnetic couplings are competing in the ground-state singlet biradical with the intramolecular antiferromagnetic interaction. The appearance of the two kinds of ground states is attributed to a quantum spin frustration effect inherent in the triangular motif of the competing interactions. Magnetic properties of a zigzag chain complex composed of a nitronyl nitroxide biradical with a singlet ground state and Cu(hfac)2 are examined on the basis of the theoretical calculations. The vanishing magnetic moments, or the product of susceptibility and temperature chiT, at low temperatures observed for the complex are consistent with those of the low-spin state predicted in the theoretical calculations. 相似文献
7.
Tanase T Doi M Nouchi R Kato M Sato Y Ishida K Kobayashi K Sakurai T Yamamoto Y Yano S 《Inorganic chemistry》1996,35(17):4848-4857
Reactions of [Ni(tren)(H(2)O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO(4) (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO(4) (2c); aldosyl = L-rhamnosyl, X(2) = SO(4) (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [Ni(II)N(4)O(2)] complex with the tren acting as a tetradentate ligand (1c.2H(2)O: orthorhombic, Pbca, a = 15.988(2) ?, b = 18.826(4) ?, c = 10.359(4) ?, V = 3118 ?(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine (2a.CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) ?, b = 20.095(4) ?, c = 8.361(1) ?, V = 2689 ?(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) ?, b = 21.823(8) ?, c = 9.746(2) ?, V = 3176 ?(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) ?, b = 21.694(5) ?, c = 9.786(2) ?, V = 3091 ?(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H(2)O)(2)]Cl(2) (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N"-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C(3) symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and (13)C NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO(4).6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N"-(L-rhamnosyl)(3)-tren)(SO(4))] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8.3CH(3)OH.H(2)O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) ?, b = 16.670(7) ?, c = 15.38(1) ?, V = 4111 ?(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C(3) symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr(2). 相似文献
8.
The novel tetranuclear copper(II) complexes with alpha-d-glucose-1-phosphates, [Cu(4)(mu-OH)(alpha-d-Glc-1P)(2)(L)(4)(H(2)O)(2)](NO(3))(3) (L = bpy (1), phen (2)), were prepared and characterized by X-ray crystallography. Complex 1 was further transformed into the ATP stabilized tetracopper(II) complex of [Cu(4)(ATP)(2)(bpy)(4)] (4), where ATP is adenosine 5'-triphosphate. 相似文献
9.
Ikeda Y Nakamura T Yorimitsu H Oshima K 《Journal of the American Chemical Society》2002,124(23):6514-6515
A cobalt complex, CoCl2[1,6-bis(diphenylphosphino)hexane], catalyzes an alkylation reaction of styrenes in the presence of Me3SiCH2MgCl in ether to yield beta-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can be employed as an alkyl source. A radical mechanism is strongly suggested for this alkylation reaction. 相似文献
10.
Tsutsumi T Amakura Y Nakamura M Brown DJ Clark GC Sasaki K Toyoda M Maitani T 《The Analyst》2003,128(5):486-492
The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish. 相似文献