Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.     

Structure of dichlorine monoxide as studied by microwave spectroscopy. Determination of equilibrium structure by a modified mass dependence method

The microwave spectra of four isotopic species of dichlorine monoxide (OCl₂) have been observed, and the rotational constants have been obtained. The r_m structure for each isotopic species has been determined by Watson's method. The equilibrium structure has been estimated by taking proper averages of r_m structures to be $\text{r}{}_{\mathrm{e}}\text{(OCl) = 1.69587(7)}\text{A}\text{?}$ and ∠_eClOCl = 110.886(6)°. The general applicability and the merit of the present method for estimating the equilibrium structure are pointed out.     

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.     

Analysis of anomalous vibrational and rotational distributions in the CN(B2Σ+) state produced in the reaction of Ar(3P0,2) metastables with BrCN

The CN(B²Σ⁺ - X²Σ⁺) tail band emission system for μ′ = 11–20 resulting from the energy transfer reaction Ar(³P_0,2) + BrCN in a flowing afterglow apparatus was measured. The vibrational and rotational distributions were determined as a function of argon pressure. Numerous perturbed rotational lines were observed; analysis of the dependences of these lines on argon pressure, with the aid of experimental information already published, led to the following assignments as to the origins of the perturbations: For μ′ = 11, N′ = 20 and μ′ = 13, N′ = 9, the perturbing state is a ⁴Σ⁺; for μ′ = 12, N′ = 10 and 14, μ′ = 14, N′ = 7 and 10, and μ′ = 17, N′ ≈ 17–19 the perturbing state is A ²Π_i. The perturbed rotational line, μ′ = 11, N′ = 20, is found to be the primary source of intensity in the μ′ =11 vibrational band, but in all other cases the perturbed rotational lines do not significantly aid in the populating of the vibrational state. The anomalously high vibrational populations found in the tail band emission system (μ′ = 12, 14, 17 and 18), as well as the significantly high rotational excitations observed in the μ′ = 12–20 vibrational bands, apparently arise directly from the reaction intermediate.     

Molecular structure of phosgene as studied by gas electron diffraction and microwave spectroscopy: The rs,rm, and re structures

The microwave spectra of eight isotopic species of COCl₂ have been observed, and the following rotational constants have been obtained: An analysis of the rotational constants has resulted in the r_s and r_m structures. The equilibrium structure, r_e, has been estimated by combining the r_m parameters derived according to Watson's method and the r_e bond distances estimated in our recent electron-diffraction and spectroscopic studies to be $\text{r}{}_{\mathrm{e}}\text{(CO}\text{) = 1.1756 ± 0.0023}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$, ∠_eClCCl = 111.79 ± 0.24°.     

Anomalies in the longitudinal ultrasonic attenuation and the velocity variation in the mixed state of a V3Si single crystal

In addition to sharp attenuation peaks of longitudinal sound waves propagating along the [001] axis of a V₃Si single crystal at the upper critical fields H_c2, new large attenuation and broad velocity peaks were observed in the mixed state. The new anomaly is explained by a mechanism related to the anisotropy of flux in the crystal tetragonally deformed by the band Jahn-Teller effect.     

Lobohedleolide and (7Z)-lobohedleolide,new cembranolides from the soft coral lobophytum hedleyi whitelegge

The structures of lobohedleolide (1) and (7Z)-lobohedleolide (2), two new cembranolides containing the α,β-unsaturated carboxylic acid system isolated from the Japanese soft coral Lobophytum hedleyi Whitelegge, were elucidated from spectral and chemical evidence, and the absolute configuration of (1) was determined by X-ray analysis of its p-bromophenacyl ester (9). Lobohedleolide (1) showed growth inhibition of the in vitro Hella cells.     

Supramolecular nanocarrier of siRNA from PEG-based block catiomer carrying diamine side chain with distinctive pKa directed to enhance intracellular gene silencing

An siRNA nanocarrier formed through self-assembly of PEG-based block catiomer possessing two distinct amino groups with different pKa values in a side chain was developed. This design provided the carrier with a sufficient siRNA complexation and an assumed buffering capacity in the endosomes, allowing it to exhibit remarkable gene knockdown abilities as well as sufficient serum tolerability.     

The first bowl-shaped stable neutral radical with a corannulene system: synthesis and characterization of the electronic structure

[structure: see text] A bowl-shaped neutral radical with a corannulene system has been designed and synthesized for the first time as a stable solid in air. An unequivocal characterization of the electronic properties of the radical shows that an appreciable amount of spin delocalization extends onto the corannulene unit's curved surface.     

Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides

1,2-Diphenyl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was used as an additive ligand in copper-catalysed amination reactions of halobenzenes with amines in the presence of base to afford the corresponding secondary or tertiary amines in good to excellent yields.