Two-dimensional imaging of atomic distribution morphology created by holographically induced mass transfer of monomer molecules and nanoparticles in a silica-nanoparticle-dispersed photopolymer film

We report an electron-probe microanalysis of a hologram recorded in a silica-nanoparticle-dispersed photopolymer film. We used S and Si atoms as label elements to identify formed polymer and nanoparticle species, respectively. It is found that the periodic density distributions of S and Si atoms are out of phase with each other, indicating that those of the formed polymer and nanoparticles are out of phase each other. This result shows decisive evidence of the mutual diffusion of monomer molecules and silica nanoparticles in the film under holographic two-beam interference exposure.     

Changes in electrochemical and optical properties of oligoalkylthiophene film induced by bipolaron formation

An unusual electrochemical response is found for oligoalkylthiophene (13T) films in acetonitrile. A pristine 13T film exhibits a stable redox wave in cyclic voltammogram when the anodic potential limit is below 0.6 V, whereas the redox peaks shift clearly to the negative side by ca. 0.1 V once the 13T film experiences a potential beyond 0.7 V. After this electrochemical stimulus is imposed on a pristine 13T film, the absorption and emission spectra change their features. These findings, along with the measurements with varying thicknesses of 13T films, suggest that a pristine 13T film is a mixture of two phases to be oxidized at separate potentials and that one phase can be switched to the other by the potential stimulation. A plausible model proposed for explaining these observations assumes that a key parameter characteristic of the two phases is a conformation of 13T molecules in the solid state and a change in conformation, leading to the shift of the redox potentials and the change of optical properties, is induced by electrochemical generation of bipolarons on the half units of the oligomers in the pristine 13T film.     

Convergent synthesis of a polyfunctionalized fullerene by regioselective five-fold addition of a functionalized organocopper reagent to C60

[reaction: see text] A method for one-step preparation of polyfunctionalized fullerene derivatives by regioselective penta-addition of an organocopper reagent is described. A functionalized aryl iodide is first converted to the corresponding Grignard reagent and then to a copper reagent and finally is allowed to react with C(60). The method allows introduction of five functional groups to the C(60) skeleton in a convergent manner. The shuttlecock-like molecules crystallize into a columnar packing structure.     

A Series of π‐Extended Thiadiazoles Fused with Electron‐Donating Heteroaromatic Moieties: Synthesis,Properties, and Polymorphic Crystals

π‐Extended thiadiazoles 4 – 8 fused with various electron‐donating heteroaromatic moieties have been designed and synthesized. Just like thiadiazoles 1 – 3 synthesized previously, 4 – 8 exhibit intramolecular charge‐transfer (CT) interactions, moderate‐to‐good fluorescence quantum yields of up to 0.78, and electrochemical amphoterism. In comparison with 1 – 3 , the benzannulation in thiadiazoles 4 – 7 moderately extends the π conjugation and significantly increases the stability of the cationic species formed upon electrochemical oxidation. The fluorescence quantum yields increase remarkably from 3 to 6 and 7 due to the efficient suppression of nonradiative intersystem crossing resulting from the benzannulation. The properties of 4 – 8 strongly reflect the different species annulated to the pyrrole rings, namely benzothiophene, naphthalene, and benzofuran. Eleven crystals, including poly‐ and pseudopolymorphic crystals of 1 ( 1‐Crys. ( Y ) and 1‐Crys. ( G )), 2 ( 2‐Crys. ( O ) and 2‐Crys. ( G )), 4 ( 4‐Crys. ( O ) and 4‐Crys. ( G )), and 6 ( 6‐Crys. ( O ) and 6‐Crys. ( G )), were obtained and characterized by X‐ray crystallography. The fluorescence colors and efficiencies are distinct for each poly‐ and pseudopolymorph of 1 , 2 , 4 , and 6 . It has been suggested that both the extent of the electronic interactions in the π‐stacked dimers and the presence of excitonic interactions originating in the 1D face‐to‐face slipped columns affect the fluorescence wavelengths of the poly‐ and pseudopolymorphs.     

Synthesis of novel blue‐light‐emitting polypyridine

A new regioregular head‐to‐tail (HT)‐type polypyridine with methoxyethoxyethoxy (MEEO) side chains, HT‐PMEEOPy, was synthesized by means of Kumada‐Tamao coupling polymerization of a Grignard monomer with a Ni catalyst. Although the polymer was precipitated in THF during polymerization, multiangle laser light scattering (MALLS) analysis indicated that the weight‐average molecular weight (M_w) was about 25,000. The HT content in the polymer was 95%. A solution of HT‐PMEEOPy in CHCl₃ was found to emit a strong blue light when the solution was irradiated with UV light; the UV‐vis absorption maximum (λ_max) and photoluminescence maximum (λ_{max em}) were at 392 and 460 nm, respectively. To clarify the effect of regioregularity of PMEEOPy on the photoluminescence, head‐to‐head (HH) PMEEOPy was synthesized by means of Yamamoto coupling polymerization. The photoluminescence of HH‐PMEEOPy (λ_max = 330 nm, λ_{max em} = 414 nm) was weaker than that of HT‐PMEEOPy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Performance of cathode-supported SOFC with Ni0.5Cu0.5–CGO anode operated in humidified hydrogen and in low-concentration dry methane

A Ni_0.5Cu_0.5–CGO (Ce_0.8Gd_0.2O_1.9) anode in a LSM ((La_0.75Sr_0.25)_0.95MnO_3?δ )–CGO cathode-supported SOFC is tested in humidified H₂ (3% H₂O) and in low concentration of dry methane, respectively. After co-sintering at 1,300?°C, it was found that the A-site-deficient LSM effectively hindered the formation of La₂Zr₂O₇ or SrZrO₃. The OCVs of the cell are as high as 1.132, 1.14, and 1.147?V in humidified H₂ and 1.314, 1.269, and 1.2?V in 14.8% of dry methane at 850, 800 and 750?°C, respectively, indicating that the ScSZ electrolyte film prepared by the present method is dense enough. The corresponding peak power densities are 0.396, 0.287, and 0.19?W?cm^?2 in humidified H₂ and 0.249, 0.164, and 0.096?W?cm^?2 in 14.8% of dry methane at 850, 800, and 750?°C, respectively. The prepared cathode-supported SOFC with NiCu–CGO bimetallic anode shows long-term stability when dry methane is used as fuel.