Stereoselective Construction of Copaborneol and Longiborneol Frameworks by Intramolecular Double Michael Reaction

Stereoselective syntheses of tricyclo[5.3.0.0(3,8)]decane 22 and tricyclo[6.3.0.0(3,9)]undecane 26, the basic skeletons of copaborneol and longiborneol, were achieved by the intramolecular double Michael reactions of 2-cyclopenten-1-ones 15-17. The substrates were prepared starting with tricyclo[5.2.1.0(2,6)]deca-4,8-dien-3-one (6). The intramolecular double Michael reactions were carried out under three different conditions: TMSCl-Et(3)N-ZnCl(2), TMSI-(TMS)(2)NH, and Bu(2)BOTf-(TMS)(2)NH. The framework 26 of longiborneol was constructed in good yields using the latter two reagent systems.     

Dual-action molecular superconductors with magnetic anions

Dual-action organic superconductors, whose conducting properties can be sharply controlled by an external magnetic field, have been discovered in systems consisting of organic conduction layers based on bis(ethylenedithio)tetraselenafulvalene (BETS) molecules and magnetic anions. Owing to the metamagnetic nature of the anion layers, the superconducting state of kappa-BETS2FeBr4 can be switched on or off by applying the external field. In lambda-BETS2Fe0.4Ga0.6Cl4, exhibiting a field-induced superconducting transition for the field parallel to the conduction plane, the insulating, metallic, and superconducting states can be realized in a stepwise manner by slightly tuning the external magnetic field.     

Effect of Composition on Surface Properties of Polydimethylsiloxane-based Inorganic/Organic Hybrid Films

Surface properties of the polydimethylsiloxane (PDMS)-based inorganic/organic hybrids films prepared from silanol-terminated PDMS and titanium tetra-isopropoxide (TIP) were investigated with an aim at the application to the thermal-fixation roll for electro-photographic printers. The 300°C-treated hybrid film with the PDMS/TIP molar ratio of 0.5 exerted a relatively high contact angle of water as 115°C. It was found by using Tapping-Mode Atomic Force Microscopy (AFM) that the hybrid film surface changed from lamella structure to sea-island structure with the increase of PDMS content when heat-treated at 150°C, and became homogenous surface over 300°C. The phase-shift detected by AFM was negative shift, showing that hybrid surface became more hydrophobic as the PDMS/TIP molar ratios of 0.35 and 4.0 exhibited excellent toner-offset property of showing no adhesion of toners, suggesting their practical use in the photographic printers.     

Directly meso-meso linked porphyrin rings: synthesis, characterization, and efficient excitation energy hopping

Directly meso-meso linked porphyrin rings CZ4, CZ6, and CZ8 that respectively comprise four, six, and eight porphyrins have been synthesized in a stepwise manner from a 5,10-diaryl zinc(II) porphyrin building block. Symmetric cyclic structures have been indicated by their very simple (1)H NMR spectra that exhibit only a single set of porphyrin and their absorption spectra that display a characteristic broad nonsplit Soret band around 460 nm. Energy minimized structures calculated at the B3LYP/6-31G* level indicate that a dihedral angle between neighboring porphyrins decreases in order of CZ6 > CZ8 > CZ4, which is consistent with the (1)H NMR data. Photophysical properties of these molecules have been examined by the steady-state absorption, fluorescence, fluorescence lifetime, fluorescence anisotropy decay, and transient absorption measurements. Both the pump-power dependence on the femtosecond transient absorption and the transient absorption anisotropy decay profiles are directly related with the excitation energy migration processes within the porphyrin rings, where the exciton-exciton annihilation time and the polarization anisotropy rise time are well described in terms of the Forster-type incoherent energy hopping model. Consequently, the excitation energy hopping rates have been estimated for CZ4 (119 +/- 2 fs)(-)(1), CZ6 (342 +/- 59 fs)(-)(1), and CZ8 (236 +/- 31 fs)(-)(1), which reflect the magnitude of the electronic coupling between the neighboring porphyrins. Overall, these porphyrin rings serve as a well-defined wheel-shaped light harvesting antenna model in light of very efficient excitation energy hopping along the ring.     

Dynamic redox systems based on bis(spiroxanthene)-type donors with a polycyclic aromatic hydrocarbon: preparation, X-ray structures, and electrochromic response with fluorescence change

The long C-C bonds (1.614(2)-1.630(2) Å) in newly prepared title donors 2-6 are cleaved upon two-electron oxidation to afford the bond-dissociated dicationic dyes 2²⁺-6²⁺, whose electron affinities are stronger than the corresponding biphenyl-2,2′-diyl dications 1²⁺ due to the spatial proximity of two xanthenylium units. Not only UV-vis but also fluorescence spectra changed drastically upon electrolysis since only colorless neutral donors are fluorescent.     

Determination of ultra-trace levels of cobalt by ion chromatographic separation and chemiluminescence detection

A luminol chemiluminescence detection/flow injection analysis technique coupled with ion chromatography (IC) has been examined for the selective determination of cobalt (II) at pg ml^?1 levels. A barium chloride solution was used as an eluent in the IC to separate cobalt(II) from interferents. When a 100-μ1 sample injection volume was used, the detection limit was 1.0 pg ml^?1 cobalt; the minimum detectable amount of cobalt was 100 fg. The calibration graph was linear above 10 pg ml^?1 and the linear dynamic range extended over six orders of magnitude. The relative standard deviation for ten replicate measurements of 30 pg ml^?1 cobalt was 3.8%. The results of the analysis of a synthetic sample corresponding to a boiling-water reactor coolant and some commercially available copper(II) standard solutions are given.     

Ultraviolet emission of molecular chlorine

The UV emission of Cl₂ from a new valence-shell state having 0⁺_u symmetry (T_c ≈ 59774 cm^?1, r_c ≈ 3.0 Å) was observed by focusing ≈ 500 nm laser radiation to gaseous chlorine. Excitation was achieved by virtual two-photon absorption from the B ³Π_0⁺u state formed by single-photon absorption stepwisely. The emission spectra showed transitions to the ground state as well as to the repulsive grade estate dissociating to Cl²P) + Cl(²P) products.     

Direct polyesterification promoted by a complex of phosphorus oxychloride with LiCl monohydrate

The reaction of benzoic acid and p-chlorophenol with phosphorus oxychloride (POC) was significantly affected by the presence of metal salt hydrates or a mixture of metal salts and water sufficiently aged. Among metal salts examined, LiCl was most effective for the reaction to give quantitative yield of the benzoate. The reaction was assumed to proceed via a complexation of POC with LiCl monohydrate followed by selective hydrolysis of POC by water bound to LiCl. The reaction promoted by a complex derived from POC and LiCl monohydrate in pyridine was successfully used as a new condensing agent for the synthesis of aromatic polyesters by the direct polycondensation or aromatic dicarboxylic acids and bisphenols. Under favorable conditions for aging of POC with LiCl monohydrate and for addition of bisphenols, polymers of moderate to high molecular weights were obtained in quantitative yield. The reaction was applied with limited success to the preparation of a copolymer of high molecular weight from hydroxybenzoic acids.     

On the structure of the radical addition product of 2-benzoxypentafluoropropene with 1,4-dioxane

The structure of the addition reaction product of 2-benzoxypentafluoropropene [CF₂ = C(CF₃)OCOC₆H₅] with 1,4-dioxane was investigated by the crystallographic analysis of the single crystal to conclude that the 2,6-disubstitution of 1,4-dioxane took place, on the contrary to the assumption that the reaction would take place at the 2- and 5-positions based on the product structure of 2-benzoxypentafluoropropene with tetrahydrofuran. Modified polyaddition reaction mechanism of bis(α-trifluoromethyl-β,β-difluorovinyl) terephthalate [CF₂ = C(CF₃)OCO-C₆H₄-COOC(CF₃) = CF₂] with 1,4-dioxane including 1,5-radical shift mechanism is proposed.