Acid-catalyzed rearrangement of aryl-substituted homobenzoquinone epoxides

The BF3-catalyzed reactions of diphenyl-substituted and endo-monophenyl-substituted homobenzoquinone epoxides proceeded through a regioselective oxirane ring opening followed by participation of a pi-aryl transannular cyclization to give the tricyclic diketo alcohols. The conformationally semirigid ethano-bridged diphenyl-substituted homologues also provided similar diketo alcohols and the subsequent ring-expanded cycloheptenedione (via a subsequent 1,2-acyl migration associated with cyclopropane ring opening), depending on the methyl-substitution pattern of the quinone frame. However, the exo-monophenyl-substituted and the rigid biphenyl-2,2'-diyl-substituted homobenzoquinone epoxides essentially remained unchanged.     

Quantum Master Equation Approach to Singlet Fission Dynamics in Pentacene Linear Aggregate Models: Size Dependences of Excitonic Coupling Effects

The singlet fission (SF) dynamics of pentacene linear aggregate models are investigated using the quantum master equation method by focusing on the Frenkel excitonic (FE) coupling effects on the SF rate and double triplet (TT) yield as well as on their aggregate size dependences. It is found that for the dimer model, unrealistically large FE couplings are needed to provide significant effects on the SF dynamics, while for the larger aggregate models a realistic FE coupling causes significant variations in the SF dynamics: as increasing the aggregate size, the SF rate rapidly increases, attains the maximum at 8-mer (~3 times enhancement as compared to the non-FE-coupling case) and then decreases, approaching a stationary value after 12-mer, although the stationary TT yield at 20-mer remains slightly smaller than that in the non-FE-coupling case. These features are explained based on the relative relaxation factors between the adiabatic exciton states. The present results contribute to constructing the design guidelines for highly efficient SF aggregates. © 2018 Wiley Periodicals, Inc.     

Spectrophotometric Determination of Polyoxyethylene Nonionic Surfactants in Ground Waters Using Triple-Stage Solid-Phase Extraction Followed by an Improved Ferric Thiocyanate Complexation Method

A practical spectrophotometric determination method for polyoxyethylene nonionic surfactants in ground waters was established, which is based on a ferric thiocyanate complexation colorimetric method preceded by a triple-stage solid-phase extraction technique using SCX, SAX, and C18 cartridges interconnected. Cationic and anionic surfactants interfere with the determination and were therefore effectively trapped and isolated by the SCX and SAX solid phases, respectively. Nonionic surfactants (NSs) were finally introduced and concentrated in the C18 cartridge. The analyte was quantitatively eluted from the C18 sorbent, and the residue was subjected to the colorimetric determination. The calibration line was linear (r² = 0.9997) up to 200µgL^–1 of heptaoxyethylenedodecylether when analyzing sample sizes of 100mL. Overall recoveries were 95–97% with an RSD of less than 3%. The method was applied to the analysis of river water, and 6.4µgL^–1 of NSs as heptaoxyethylenedodecylether was found by means of the standard addition method. The proposed method is very practical and features minimum consumption of chemicals.     

Alkali effects on the electronic states of K3C60 and Rb3C60

The electronic states in metallic alkali fullerides K₃C₆₀ and Rb₃C₆₀, are studied in detail by cw- and pulsed-ESR. The ESR linewidth associated with conduction electrons varies substantially, depending sensitively on the alkali metals used. It is clearly revealed that the linewidth is homogeneous and is strongly controlled by the spin-lattice relaxation times (T₁) determined via the spin-orbit interactions of the small fraction of s electrons remaining on the alkali atoms. The results indicate that the electron transfer from the alkali atoms to C₆₀ is not perfectly complete, with the remaining fraction being much greater in the tetrahedral sites than in the octahedral sites of the face-centered cubic lattice.     

Hybrid density functional theory studies on the magnetic interactions and the weak covalent bonding for the phenalenyl radical dimeric pair

The phenalenyl radical (1) is a prototype of the hydrocarbon radical. Recently, the single crystal of 2,5,8-tri-tert-butylphenalenyl (2) was isolated and showed that the two phenalenyl radicals form a staggered dimeric pair, giving rise to strong antiferromagnetic interactions. The origin of the antiferromagnetic interactions and the nature of the chemical bond for the dimeric pair are challenging issues for chemists. First, spin-polarized hybrid DFT (Becke's half and half LYP (UB2LYP)) and CASSCF calculations were performed for 2 and its simplified model, the staggered-stacking phenalenyl radical dimeric pair (3a), to elucidate the origin of the strong antiferromagnetic coupling and the characteristics of the chemical bond. The calculated results showed that a SOMO-SOMO overlap effect was responsible for the strong antiferromagnetic interactions and weak or intermediate covalent bonding between phenalenyl radicals. The tert-butyl groups introduced at three beta-positions hardly affected the magnetic coupling, mainly causing steric hindrances in the crystalline state. Next, to obtain insight into ferromagnetic stacking, we investigated the stacking effect of staggered (3a)- and eclipsed (3b)-stacking phenalenyl radical dimeric pairs with a change of the SOMO-SOMO overlap on the basis of the extended McConnell model. We found that the stacking mode of the dimeric pair with both a small SOMO-SOMO overlap and a ferromagnetic spin polarization effect provided a ferromagnetic coupling.     

Conformational effects in acid-mediated ring opening of epoxides: a prominent role of the oxirane Walsh orbital

A kinetic study has been made of the BF(3)-mediated ring opening of two rigid conformers (alpha and beta) of m- and p-dimethyl-substituted homobenzoquinone epoxides spiro-linked with a twist-boat dibenzocycloheptene ring as compared with the conformationally mobile epoxides bearing diphenyl groups. The rates of the regioselective ring opening were dependent on the topological alignment of the dibenzocycloheptene ring as well as the substitution pattern of the quinone dimethyl groups, indicating pi-aryl participated orbital interaction with the vacant Walsh orbital of the oxirane ring.     

Simultaneous determination of mean pressure and deviatoric stress based on numerical tensor analysis: a case study for polycrystalline x-ray diffraction of gold enclosed in a methanol-ethanol mixture

It is known that the {100} and {111} planes of cubic crystals subjected to uniaxial deviatoric stress conditions have strain responses that are free from the effect of lattice preferred orientation. By utilizing this special character, one can unambiguously and simultaneously determine the mean pressure and deviatoric stress from polycrystalline diffraction data of the cubic sample. Here we introduce a numerical tensor calculation method based on the generalized Hooke's law to simultaneously determine the hydrostatic component of the stress (mean pressure) and deviatoric stress in the sample. The feasibility of this method has been tested by examining the experimental data of the Au pressure marker enclosed in a diamond anvil cell using a pressure medium of methanol-ethanol mixture. The results demonstrated that the magnitude of the deviatoric stress is ～0.07?GPa at the mean pressure of 10.5?GPa, which is consistent with previous results of Au strength under high pressure. Our results also showed that even a small deviatoric stress (～0.07?GPa) could yield a ～0.3?GPa mean pressure error at ～10?GPa.     

Spin physics in the high energy hadron productions —A systematic study of the spin asymmetries induced by pp, γp, ep and νp collisions

The spin polarizations of hadrons inclusively produced by pp, γp and νp collisions are studied by the quark rearrangement model. The present model is a phenomenological one based on the relativistic spin equations of motion and using the quark distribution functions in hadrons and photon. A general success of the model is demonstrated. We find usefulness of the present formulation for studying the dynamics producing spin asymmetry distributions and the statics determining signs and magnitudes of the spin polarization by reflecting the characteristic quark structure in hadrons.     

Development and application of parallel-plate avalanche counter for in-beam Mössbauer spectroscopy

For Mössbauer -rays in the in-beam Mössbauer experiments using various beams such as heavy ion, secondary short-lived isotope, and neutron beams, it is important to develop a detector. A parallel-plate avalanche counter (PPAC) is the most suitable gas counter for on-line measurements, because PPAC collects the internal conversion electrons emitted by the Mössbauer effect even under high -background. We evaluated the influences of the pressure and flow rate of the counter gas against the counting efficiency of PPAC, and determined the optimum conditions for use in the in-beam Mössbauer experiments.