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81.
Sotoyama W Satoh T Sato H Matsuura A Sawatari N 《The journal of physical chemistry. A》2005,109(43):9760-9766
The absorption and emission spectra of the Pt(II) complexes containing N wedge C wedge N-coordinating tridentate ligands, platinum(II) 1,3-di(2-pyridyl)benzene chloride [Pt(dpb)Cl] and platinum(II) 3,5-di(2-pyridyl)toluene chloride [Pt(dpt)Cl], together with their corresponding free ligands, 1,3-di(2-pyridyl)benzene (dpbH) and 3,5-di(2-pyridyl)toluene (dptH), have been analyzed by density functional theory (DFT) for the ground state and time-dependent DFT (TDDFT) for the excited states. T(1)(A(1)) and S(1)(B(2)) of the complexes (in C(2)(v) symmetry) were assigned on the basis of the calculated excitation energies as well as comparison of the experimental spectroscopic properties and the calculated states' characteristics. The calculated excitation energies for T(1) and S(1) of the complexes as well as those for T(1) of the free ligands were in good agreement with their observed values within 600 cm(-1). The d-pi* characters of the excited states were evaluated from the change in electron densities between the ground and excited states by Mulliken population analysis; values of 25% for T(1) and 32% for S(1) were obtained for both complexes. The calculated values of d-pi* character were found to be consistent with the reported emission lifetimes as well as the observed emission energy shifts from the corresponding free ligands. Most spectroscopic properties of the complexes and the free ligands, which include solvatochromic shift, Stokes shifts, methyl substitution shifts, and emission spectra profiles, were well explained from the calculation results. 相似文献
82.
Sato H Tashiro K Shinmori H Osuka A Murata Y Komatsu K Aida T 《Journal of the American Chemical Society》2005,127(38):13086-13087
Upon binding with C60 and diamines, such as 4,4'-bipyridine (bpy) and N,N,N',N'-tetramethylhexane-1,6-diamine (TMHDA), cyclic host 1 possessing two electronically coupled binding sites displays negative homotropic cooperativity and positive heterotropic cooperativity, and their ternary mixtures preferentially form inclusion complexes with hetero-guest pairs 1 supersetC60*bpy and 1 supersetC60*TMHDA under appropriate conditions. Spectroscopic titration profiles in toluene at 20 degrees C demonstrated that the association constants (Kassoc) of C60 with monodiamine complexes 1 supersetbpy (2.8 x 105 M-1) and 1 supersetTMHDA (1.5 x 105 M-1) are 8.5 and 4.5 times greater than that of C60 with guest-free 1 (3.3 x 104 M-1), respectively. On the other hand, mono-C60 complex 1 supersetC60 was 6.1 times more accessible than guest-free 1 toward TMHDA. Absorption spectroscopy in the absence of 1 indicated no direct interaction between C60 and diamines. 相似文献
83.
Mori M Saito N Tanaka D Takimoto M Sato Y 《Journal of the American Chemical Society》2003,125(19):5606-5607
Novel alkenylative cyclization of enyne was developed using Cp*RuCl(cod) under ethylene gas at room temperature. 相似文献
84.
Copper mediated alkyl-transfer reaction of trialkylaluminum (R3Al) with (E)-4,4-difluoro-5-hydroxyallylic alcohol derivative smoothly proceeded to give the corresponding 2-alkylated 4-fluoro-5-hydroxyhomoallylic alcohol derivative with completely Z and 2,5-syn selective manner. Regio- and stereoselective conversion of the C5-hydroxyl group of the fluoroolefin thus obtained to amino group could be achieved through one-pot mesylation and azidation reaction. 相似文献
85.
[reaction: see text] A concise and stereoselective synthesis of the chiral building block, dioxanylpiperidene 4 as a precursor for deoxyazasugars, starting from the Garner aldehyde 5 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring is described. The asymmetric synthesis of 1-deoxygalactonojirimycin and its congeners 1-3 was carried out via the use of 4 in a highly stereocontrolled mode. 相似文献
86.
Bowl‐shaped chiral homotriazacalixarenes were prepared by the cyclization reactions of chiral triamines with three equimolar amounts of bis(chloromethyl) phenols or bis(chloromethyl) phenol‐formaldehyde dimers in moderate yields. The corresponding acyclic phenol‐formaldehyde oligomers were also synthesized. The structural analysis of the macrocycles by nmr and circular dichroism spectra imply the existence of chiral transmission from the point chirality of the cysteine bridge to the cyclophane moiety. Their cyclic and acyclic compounds have a π‐base cavity large enough to include the ammonium ion. 相似文献
87.
The change in fluidity by adding pentoxifylline to erythrocyte membranes was compared with that caused by S-adenosyl-L-methionine (SAM) by the method of electron spin resonance (ESR) spectroscopy. When SAM or pentoxifylline was added externally to the erythrocyte suspension (outside), the fluidity of the membrane bilayer was increased after incubation at 37 degrees C. However, the fluidity change in the inner part of the bilayer was relatively small compared to that in its outer part. These fluidity changes were dependent on the incubation time and the temperature. When the erythrocyte suspension was preincubated overnight at 4 degrees C in the presence of drugs (inside), the fluidity of the inner part of the membrane changed significantly. Nevertheless, that of the outer part of the lipid bilayer was not affected. Such an asymmetric fluidity change in the lipid bilayer was not observed by the addition of other xanthine derivatives such as caffeine, theophylline and theobromine. S-Adenosyl-L-homocysteine suppressed and MgCl2 enhanced the increase of the membrane fluidity by SAM or pentoxifylline. Furthermore, the effects of SAM and pentoxifylline on erythrocyte deformability were determined by a filtering technique method. In increasing order the additive effects of SAM and pentoxifylline on the erythrocyte filterability were SAM (outside) less than pentoxifylline (inside) less than pentoxifylline (outside) less than SAM (inside). These results suggest that pentoxifylline also affects the membrane fluidity through the enzymatic methylation of phospholipids. 相似文献
88.
Toshio Takido Sachiko Tamura Kenji Sato Haruo Kamijo Toshikatsu Nakazawa Manabu Seno Tadashi Hata 《Journal of heterocyclic chemistry》1998,35(2):437-443
The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X2 = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated. 相似文献
89.
The synthesis of an asymmetric glycocluster 1 has been achieved by coupling of a sugar unit with the β-alanine polypeptide, the principal chain, and combining a carbohydrate chain with the side chain causing it to branch from the N terminal. The synthesis of this side chain multivalent ligands is based on the scaffolding of some ω-amino acid (glycine, β-alanine, and GABA) derivatives. This method facilitated the synthesis of the cluster, of which the length of each unit differs. 相似文献
90.