C-S bond cleavage of pyridine-2-thiol: a new functionality of quadruply bridged dinuclear platinum and palladium complexes

Treatment of pyridine-2-thiol (pytH) with H(2) (60 atm) in the presence of 5-methylpyridine-2-thiolate (5-mpyt)-bridged dinuclear Pt(III), Pt(II), or Pd(II) complexes (1 mol %) in DMF at 150 degrees C for 72 h leads to the formation of pyridine in 3-51% yield. From the (1)H NMR study of the exchange reactions and of the products under D(2) pressure, it is suggested that the catalytic reaction involves bimetallic activation of the pyt ligand followed by the liberation of pyridine and H(2)S.     

Isotope-dependent crystalline phases at ambient temperature: Spectroscopic and calorimetric evidence for a deuteration-induced phase transition at 320 K in α-DCrO2

The heat capacities of HCrO₂ and DCrO₂ have been measured at temperatures between 5 and 360 K. A lambda anomaly occurred at 320 K for DCrO₂ but not for HCrO₂. Infrared spectra were recorded at temperatures between 5 and 405 K. The spectrum of DCrO₂ changed at 320 K with respect to the peak wave-number and splitting of some of the vibrations, while those of HCrO₂ depended smoothly on temperature. These experimental results are discussed in terms of a deuteration-induced phase transition.     

A novel synthesis of half-protected 1,3-dicarbonyl compounds

It has been found that the reaction of enol silyl ethers with 2-ethoxy-1,3-dithiolane proceeds smoothly in the presence of zinc chloride catalyst to afford half-protected 1,3-dicarbony1 compounds in moderately good yields.     

Evidence for muon neutrino oscillation in an accelerator-based experiment

We present results for nu(mu) oscillation in the KEK to Kamioka (K2K) long-baseline neutrino oscillation experiment. K2K uses an accelerator-produced nu(mu) beam with a mean energy of 1.3 GeV directed at the Super-Kamiokande detector. We observed the energy-dependent disappearance of nu(mu), which we presume have oscillated to nu(tau). The probability that we would observe these results if there is no neutrino oscillation is 0.0050% (4.0 sigma).     

Aggregation states and surface wettability in films of poly(styrene-block-2-perfluorooctyl ethyl acrylate) diblock copolymers synthesized by atom transfer radical polymerization

Well-defined poly(styrene-block-2-perfluorooctyl ethyl acrylate) [P(St-b-PFA)] copolymers with various chemical compositions were synthesized by atom transfer radical polymerization. Films of P(St-b-PFA) were structurally characterized, from bulk to surface, on the basis of transmittance electron microscopic observation and small-angle X-ray scattering, X-ray photoelectron spectroscopic, and contact angle measurements. For a comparison, poly(styrene-random-2-perfluorooctyl ethyl acrylate) [P(St-ran-PFA)] copolymers were also synthesized by conventional free radical polymerization. While P(St-b-PFA) with the 2-perfluorooctyl ethyl acrylate (PFA) content higher than 18.7 mol % formed a typical phase-separated cylinder structure, P(St-b-PFA) with a lower PFA content and P(St-ran-PFA) were in a miscible state. Since the perfluoroalkyl groups possess extremely low surface energy, they were preferentially segregated at the film surface, resulting in the formation of the PFA surface layer. This was the case for all P(St-b-PFA) films examined, although the aggregation state at the surface was strongly dependent on the PFA content. In the case of the P(St-b-PFA) with the PFA content higher than 18.7 mol %, both advancing and receding contact angles for water were 120 degrees and even larger with almost no hysteresis. In addition, extremely excellent oil-repellent surface properties such as advancing and receding contact angles for dodecane of 76 degrees and 75 degrees were also observed. However, these intriguing liquid-repellent properties were not observed for the films of miscible P(St-b-PFA) and P(St-ran-PFA). Therefore, it can be concluded that the internal structure beneath the surface as well as the surface itself should be deeply considered to design excellent and stable liquid-repellent materials.     

Single-particle light scattering study of polyethyleneglycol-grafted poly(ureaurethane) microcapsule in ethanol

Microcapsules having polyethyleneglycol-grafted poly(ureaurethane) (PUU) membrane and di-2ethylhexyl phthalate core have been prepared, and the structure when they were suspended in dispersing ethanol have been studied by means of single-particle light scattering method. The PUU membrane was synthesized from monomers with aromatic functional groups (microcapsule MC110) and hexamethylene functional groups (microcapsule MC160). Because the outer and inner solvent passed through the membrane easily, the outside and inside of the membrane were the same at the equilibrium state. The thickness of the wall membrane was significantly smaller than that calculated from the overall weight ratio of the wall-forming material and the core solvents. It was attributed to low affinity of PUU membranes and ethanol.     

Creation of hoop- and bowl-shaped benzenoid systems by selective detraction of [60]fullerene conjugation. [10]cyclophenacene and fused corannulene derivatives

Selective penta-addition of a methylcopper reagent followed by addition of a phenylcopper reagent to a suitably modified synthetic intermediate results in creation of 40pi-electron systems-hoop- and bowl-shaped cyclic benzenoid compounds, [10]cyclophenacene, and dibenzo-fused corannulene derivatives. The 40pi-electron cyclophenacene derivatives have been found to be chemically stable, yellow-colored, luminescent (560 nm), and EPR-silent. X-ray crystallographic analysis provided precision structural data sets. The dibenzo-fused corannulene derivatives exhibit blue-green (460 nm) to red (649 nm) fluorescence.     

Molecular optical gating devices based on polymer nanosheets assemblies

We describe here a polymer nanosheet assembly that serves as a molecular photoswitching and optical exclusive OR (EXOR) logic gate. Separate polymer nanosheets (monolayers) containing phenanthrene, anthracene, and dinitrobenzene chromophore were prepared by the Langmuir-Blodgett technique (LB films). A bilayer-couple, consisting of phenanthrene (sensitizer) monolayer and dinitrobenzene (acceptor) monolayer, and the other couple, of anthracene monolayer and dinitrobenzene monolayer, were confirmed to function as a photodiode showing current rectification on light irradiation. The two photodiodes are connected as each photocurrent direction becomes opposite. In the polymer photodiode array (LB films), anodic photocurrent was observed when the anthracene was selectively excited. On the other hand, cathodic photocurrent was observed by selective excitation of the phenanthrene. Moreover, the output photocurrent displayed a very small value when the phenanthrene and anthracene were excited simultaneously. The performance is discussed for this gate's application to an optical EXOR logic gate.     

1,8-bis(diphenylmethylium)naphthalenediyl dication as an organic oxidant: synthesis of benzidines via self-coupling of N,N-dialkylanilines

1,8-Bis(diphenylmethylium)naphthalenediyl dications promoted oxidative coupling of various N,N-dialkylanilines to afford the corresponding para-coupled bisanilines, benzidines, in good to excellent yield. The dications were readily prepared from a cyclic ether precursor, derived from 1,8-dibromonaphthalene, via deoxygenation with a silylating reagent in 1,1,1,3,3,3-hexafluoro-2-propanol under anhydrous conditions. [reaction: see text]