Palladium-catalyzed multiple arylation of thiophenes

Secondary 2-thiophenecarboxamides efficiently undergo unique triarylation accompanied by formal decarbamoylation under palladium catalysis. 3-Substituted thiophenes, especially having an electron-withdrawing group, can also be triarylated.     

Hyperfine structure of the electron spin resonance of phosphorus-doped Si nanocrystals

Electronic states of P donors in Si nanocrystals (nc-Si) embedded in insulating glass matrices have been studied by electron spin resonance. Doping of P donors into nc-Si was demonstrated by the observation of optical absorption in the infrared region due to intraconduction band transitions. P hyperfine structure (hfs) was successfully observed at low temperatures. The observed splitting of the hfs was found to be much larger than that of the bulk Si:P and depended strongly on the size of nc-Si. The observed strong size dependence indicates that the enhancement of the hyperfine splitting is caused by the quantum confinement of P donors in nc-Si.     

Theory of ferromagnetism in Ca(1-x)La(x)B(6)

Novel ferromagnetism in Ca(1-x)La(x)B(6) is studied in terms of the Ginzburg-Landau theory for excitonic-order parameters, taking into account symmetry of the wave functions. We found that the minima of the free energy break both inversion and time-reversal symmetries, while the product of these two remains preserved. This explains various novelties of the ferromagnetism and predicts a number of magnetic properties, including the magnetoelectric effect, which can be tested experimentally.     

Representation of the category of tangles by Kontsevich's iterated integral

Applying Kontsevich's iterated integral for tangles, we get an isotopy invariant of tangles. We give a method to compute the integral of a tangle combinatorially from modified integrals of some simple tangles. We localize the integral by moving the end points of the tangle to an extreme configuration, and modify the integral so that it is convergent. By using a similar technique, we generalize Kontsevich's invariant to a framed tangle.     

Selective removal of tetrahydropyranyl ethers in the presence of t-butyldimethylsilyl ethers

Dimethylaluminiun chloride has been found to cleave THP ethers selectively without any removal of t-butyldimethylsilyl ethers     

Phase diagram analysis using a partially associated solution model for III–V binary systems

Some of the physical and thermodynamic properties of III–V liquids can be explained by assuming that the liquids have a dual structure. The thermodynamic model which has been established for the present paper is a partially associated solution model. It was constructed on the assumption of the existence of associated complexes. The asymmetry of the liquidus curve and the amount of excess free energy determined from the phase diagram analysis can be explained by using the model. Some of the thermodynamic parameters obtained in this study are found to have important physical meanings. The interaction parameter between monoatomic species, ω_A,B is in a good agreement with the theoretical value proposed by Stringfellow. The heat of formation of associated complexes can be represented explicitly in terms of the spectroscopic ionicity and the dehybridization factor. The free energy of formation is empirically evaluated to be 20-6(f_i ?0.17)RT?35,000f_iDcal/mol for III–V binary liquids.     

Formation of cyclic organosilicon compounds via organopolysilyl anions starting from methoxymethyldisilanes. A mechanistic study

In the presence of a catalytic amount of sodium methoxide, sym-dimethoxytetramethyldisilane was converted into α,ω-dimethoxypermethylpolysilanes, MeO(SiMe₂)_nOMe where n ? 3, at room temperature. On the other hand, similar treatment of the disilane in THF solution gave cyclic polysilanes, (Me₂Si)_n where n = 5–7. Decomposition of the disilane in the presence of diphenylacetylene afforded a trisilacyclopentene derivative under similar conditions. This compound was obtained also by the reaction between α,ω-dimethoxypermethylpolysilanes and diphenylacetylene in the presence of sodium methoxide. These cyclic products most likely were formed via permethyl polysilyl anion intermediates derived from α,ω-dimethoxypermethylpolysilanes. Also, the formation of α,ω-dimethoxypermethylpolysilanes could be elucidated in terms of the mechanism involving the base-assisted, concerted nucleophilic substitution or stepwise substitution by silyl anions, rather than the successive dimethylsilylene (Me₂Si:) insertion reaction.     

Real-time charge oscillation between monomers in a dimeric system associated with intermolecular vibration induced by an ultrashort pulse

Ultrafast charge resonant (CR) dynamics between two molecules in a dimer system has been studied theoretically and experimentally using 6-fs laser pulses and a thin film of amorphous-phase phthalocyanine tin(IV) dichloride (SnPc). The modulation of the absorbance change in the bleaching spectral range of the CR absorption band was analyzed to obtain the amount of charge resonantly transferred back and forth by a dimeric vibration induced by photoexcitation. The modulation can be explained in terms of a periodic change in the cross section and a periodic energy shift, where both are induced by the change in the overlap integral caused by the accordion-type intermolecular vibration. The associated change in distance between two molecules with the intermolecular vibration was estimated to be 0.09 A, which corresponds to 2.5% of the mean distance between the two SnPc molecules in the dimeric system.