Titanium-silicon (Ti/Si) binary oxides having different Ti contents were prepared by the sol-gel method and used as photocatalysts. The photocatalytic reactivity of these catalysts was investigated as a function of the Ti content for the liquid-phase oxidation of 1-octanol to 1-octanal, and it was found to be dramatically enhanced in regions of lower Ti content. In situ photoluminescence, UV-vis reflectance, FT-IR, ESR, XAFS, XRD, and XPS spectroscopic investigations of these Ti/Si binary oxides indicated that the titanium oxide species are highly dispersed in the SiO 2 matrixes and exist in a tetrahedral coordination exhibiting a characteristic photoluminescence spectrum due to the radiative decay from the charge-transfer excited state of the tetrahedrally coordinated titanium oxide species. The good parallel relationship between the yield of the photoluminescence and the specific photocatalytic reactivity of the Ti/Si binary oxides as a function of the Ti content clearly indicates that the high photocatalytic reactivity of the Ti/Si binary oxides having a low Ti content is associated with the high reactivity of the charge-transfer excited state of the isolated titanium oxide species in tetrahedral coordination, [Ti 3+ -O -]*.

Several poly(arylene thioether)s (PTEs) containing a fluorene moiety were synthesized by the polycondensation of masked dithiols such as 9,9‐bis(4‐(N,N‐dimethyl‐S‐carbamoyl)phenyl)fluorene and various difluoroarenes. All PTEs were obtained in quantitative yields. The PTEs showed good thermal stability: the 10% weight loss temperature was over 480 °C under both nitrogen and air atmosphere by TGA, and glass temperature was within a range of 204–275 °C by DSC. Most PTEs exhibited remarkably high refractive index values in a range of 1.66–1.72 at 589 nm, whereas they had a very low degree of birefringence properties. Furthermore, the PTEs showed high solubility in ordinary organic solvents such as chloroform, N‐methylpyrrolidone, and tetrahydrofuran. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3073–3082, 2007

The electroreduction of alkylaryldichlorosilane carried out with Mg cathode and anode in a single compartment cell gave high molecular weight poly(alkylarylsilane) (M(n) = 5200-31000, M(w)/M(n) = 1.4-1.8) in 5-79% yield. The effects of electrode material, monomer concentration, amount of supplied electricity, and ultrasound were investigated. This electroreductive method was also successfully applied to the synthesis of polygermanes, silane-geramane copolymers, and also poly[p-(disilanylene)phenylenes].

Fluorene-based poly(ether-ether-ketone) (F-PEEK) was designed and synthesized by reacting a 9,9-diarylfluorene-containing biphenol and a naphthalene-containing dihaloarene. High molecular weight F-PEEK (M w > 270 000; M n ∼ 55 000) was obtained in quantitative yields by the two-step polycondensation of 9,9-bis-(4-hydroxy-3-methylphenyl)fluorene and 1,5-bis(4-fluorobenzoyl)-2,6-dimethylnaphthalene in the presence of cesium carbonate in diphenyl sulfone at 165 °C and then 220 °C. The chemical, physical, and optical properties of F-PEEK were evaluated. Good solubility of F-PEEK in ordinary organic solvents such as THF and chloroform was confirmed. F-PEEK exhibited a high refractive index of 1.64 at 589 nm, whereas it showed a much lower birefringence value than a polycarbonate or a polyester. F-PEEK was amorphous and transparent at room temperature. The transmittance of F-PEEK in film state was over 80% in the visible region. These optical properties were probably related to the cardo structure of the fluorene moiety placed on the main chain. No phase transition except for T g was confirmed in the DSC analysis. F-PEEK displayed a high storage modulus (E′ ) 2.93 GPa) and glass transition temperature (280 °C) in comparison with commercially available poly(ether-ether-ketone) (PEEK, E′ ) 1.73 GPa and T g 169 °C). The high modulus of F-PEEK was derived unambiguously from both the fluorene and naphthalene skeletons.