Reductive Benzylation of Dimetallo Hexaaryl[70]Fullerenes on the Equatorial Region

Dianions of dimetallic hexa(organo)[70]fullerene [(C₅R₅)₂Ru₂C₇₀Ar₆]^2? (R=H, Me; Ar=Ph, 4‐MeC₆H₄, 4‐tBuC₆H₄) react with benzylic bromide to yield the dibenzylated product dimetallic octa(organo)[70]fullerene (C₅R₅)₂Ru₂C₇₀Ar₆(CH₂Ar′)₂ (Ar′=Ph, 4‐MeO₂CC₆H₄), where the benzylic groups are attached to the equatorial belt region of [70]fullerene; this region is generally considered to be rather unreactive. This unusual structure was unambiguously determined by X‐ray crystallography. Theoretical studies on the electronic properties of the monoanionic intermediate indicated that the highest spin density resides on the two carbon atoms in the belt region; one of them then couples with a benzylic radical to yield the octa(organo)fullerene product after ionic substitution of the fullerene anion with a benzylic bromide. Electrochemical analysis of the hexa(organo) and octa(organo) ruthenium complexes suggests that the modification of the belt region does not affect the electronic communication between the two metal centers.     

Modular Synthesis of Polybenzo[b]silole Compounds for Hole‐Blocking Material in Phosphorescent Organic Light Emitting Diodes

A diversity‐oriented synthetic strategy allowed us to design a series of conjugated molecules containing multiple benzosilole units that can be utilized as efficient hole‐blocking materials for phosphorescent organic light emitting diodes (OLEDs). Some of these compounds showed a performance surpassing that of the current standard, bathocuproine. The new compounds were easily synthesized in a modular fashion from a previously reported 3‐stannyl benzosilole building unit. Studies on the properties of these compounds in solution and in the solid state indicate that they possess high electron affinity, high ionization potential, and form stable amorphous films that show high electron‐drift mobility. The correlation between their molecular properties and the efficiency of the OLED device performance is also investigated.     

Tight Relative 2- and 4-Designs on Binary Hamming Association Schemes

The concept of relative t-designs for Q-polynomial association schemes is due to Delsarte (Philips Res Rep 32:373–411, 1997). We formulate Fisher type lower bounds as well as the concept of tight relative 2- and 4-designs very explicitly for binary Hamming association schemes H(n, 2). Then we discuss some examples of tight relative 2- and 4-designs on H(n, 2) in this sense, in connection with the work of Woodall (Proc Lond Math Soc (3) 20:669–687, 1970), Enomoto-Ito-Noda (Osaka J Math 16:39–43, 1979), and others. The present paper is expected to be the first of a series of our studies of tight relative t-designs on Q-polynomial association schemes in a more general context.     

Development in fission track-thermal ionization mass spectrometry for particle analysis of safeguards environmental samples

An improved method of fission track (FT) sample preparation was developed, in which the detector of fission track and the layer containing particles are separated, in order to apply the FT-thermal ionization mass spectrometry (TIMS) for particle analysis of safeguards environmental samples. The developed FT sample enabled us to detect the particle of interest simply by observing the fission tracks. The process of particle identification was difficult due to the discrepancy between the position of the particles and fission tracks, which were observed in the conventional FT sample. The proposed method has significantly resolved this problem.     

Phase transition of layer structure of poly(p-benzenedithiol-co-p-diethynylbenzene) by heat or photon mode

Phase transition of the layer structure of poly(p-benzenedithiol-co-p-diethylbenzene) obtained in solid state polymerization was studied by a thermal treatment or UV irradiation under a nitrogen atmosphere. The peak intensities in the X-ray diffraction diagram of polymers gradually decreased with the thermal treatment time above 55°C. Below 50°C the layer structure of polymers hardly changed. The apparent activation energy for the phase transition was about 15 Kcal/mol [63 KJ/mol] at the initial stage and gradually decreased to a few Kcal/mol [ca. 2 KJ/mol]. UV light from a high-pressure mercury lamp also gradually induced the phase transition from the layer structure to an amorphous one. The pristine polymer possesses phase transition points at 75, 95 and 130°C. The exothermic transition at 75°C can be understood as the thermal destruction of the semistable layer structure. The exothermic transition at 95°C may be correspond to the cis → trans thermal isomerization of the C?°C bond in the polymer main chain. The diffuse reflectance spectrum of the pristine polymer differed from that of the amorphous polymer obtained by the thermal treatment of the pristine polymer. SEM photographs of the pristine polymer showed a particular surface structure, i.e. entangled fibrous material. TEM photographs of the pristine polymer exhibited a bright valley-and-hill structure, whereas that of the amorphous polymer obtained by thermal treatment exhibited a plain surface.     

丝光沸石复合膜的制备及其影响因素

采用在多孔氧化铝支撑体上预涂纳米丝光沸石晶种,再用水热晶化的方法制备丝光沸石复合膜.系统考察了反应母液陈化、碱度、盐以及反应温度等因素对丝光沸石晶体在预涂晶种支撑体上成膜化过程的影响.研究发现,膜表面晶体间空隙随反应母液陈化时间的增加而略有增大;高碱度的反应母液不利于连续丝光沸石复合膜的形成;反应母液中盐的浓度对丝光沸石晶体沿各个轴方向上的生长速率有不同程度的影响,膜表面晶体间空隙随盐浓度的增加而增大;晶化温度过高,容易形成细棒状晶体,导致晶体间空隙增大.     

Scaling of anomalous hall resistivity in Nd2(Mo(1-x)Nb(x))2O7 with spin chirality

We have investigated scaling of anomalous Hall resistivity with longitudinal resistivity (rho(xx)) in pyrochlore type Nd2(Mo(1-x)Nb(x))2O7 with spin chirality. Scattering rate of the conduction electron on the Mo sublattice can be varied with x from band transport to polaron hopping, while keeping the two-in-two-out structure of the Nd moments intact. The anomalous part of the Hall resistivity arising from the Mo spin chirality (rho(H)(chi)) shows a clear scaling behavior with rho(xx) (rho(H)(chi) proportional to rho(xx)0.39), in accord with a recent theoretical result based on the Berry phase mechanism in the hopping conduction regime.     

Synthesis of functionalized 1H-indenes via copper-catalyzed arylative cyclization of arylalkynes with aromatic sulfonyl chlorides

A variety of polysubstituted 1H-indenes can be prepared through the copper-catalyzed arylative cyclization of simple arylalkynes with commercially available aromatic sulfonyl chlorides that function as an aryl group donor. The reaction tolerates a broad range of functional groups, including bromide and iodide, nitrile, ketone, and nitro groups. The reaction allowed the synthesis of polycyclic aromatic hydrocarbons, such as a bis(indene), indacene, and fused polyarene derivatives, some of them showing strong fluorescence in solution and the solid state.     

A divergent synthesis of dihydropyridazinones,N‐substituted dihydropyrazoles,and O‐substituted pyrazoles

Dihydropyridazinones 4a , 4b , N‐substituted dihydropyrazoles 5b , 5c , 5d , and O‐substituted pyrazoles 6a , 6b , 6c , 6d have been synthesized starting from spirocyclopropanepyrazole derivative 2 . Treatment of 2 with α‐chloro esters, e.g., methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate, and tert‐butyl chloroacetate, in potassium carbonate/sodium iodide system caused ring opening and subsequent C‐ or N‐attack nucleophilic substitution to give the corresponding dihydropyridazinones 4a , 4b and N‐substituted dihydropyrazoles 5b , 5c , 5d . On the other hand, in the absence of sodium iodide, O‐substituted pyrazoles 6a , 6b , 6c , 6d were obtained from 2 via an O‐attack nucleophilic substitution. J. Heterocyclic Chem., 2011.