Observation of Exceptionally Low-Lying π-π* Excited States in Oxidized Forms of Quadruple-Decker Phthalocyanine Complexes

Spectroscopic investigations have been performed for the oxidized forms of two quadruple-decker phthalocyanine complexes in order to clarify the electronic structures of multiply stacked π-systems. Up to three-electron-oxidized species were isolated by using phenoxathiin hexachloroantimonate as the oxidant. As the oxidations proceed, the Q-bands in the visible region shift bathochromically along with the clear isosbestic points. The one- and three-electron-oxidized species exhibited typical π-radical signals in the ESR spectra, while the neutral and two-electron oxidized species gave no indication of the presence of π-radicals. The electronic transitions observed for the oxidized species reach even into the so-called fingerprint region in IR spectroscopy (～1000 cm(-1)). With the aid of theoretical calculations, these bands can be assigned to the π-π* transitions. Our results provide new insights into π-electronic systems having exceptionally small MO energy gaps.     

Conformity and precision of CO2 densimetry in CO2 inclusions: microthermometry versus Raman microspectroscopic densimetry

To assess the ability of densimetry for CO₂ fluid in CO₂ inclusions, we compare two methods, microthermometry and Raman microspectroscopic densimetry for CO₂. The comparative experiment was performed for nine CO₂ inclusions in three mantle xenoliths. The results are as follows: (1) microthermometry precisely determines CO₂ density with the range of 0.65 to 1.18 g/cm³ compared with Raman microspectroscopic densimetry; (2) CO₂ density obtained by Raman microspectroscopic densimetry is fairly consistent with that by microthermometry; (3) it is hard to determine CO₂ density in CO₂ inclusion with diameter of less than around 3 µm using microthermometry; and (4) microthermometry can be applied only to the CO₂ inclusion whose CO₂ density ranges from around 0.65 to 1.18 g/cm³, whereas the Raman microspectroscopic densimetry is applicable to CO₂ density ranging from 0.1 to 1.24 g/cm³. The above features carry the potential for estimation of depth origin of mantle‐derived rocks. The depth where the rocks were trapped by host magma can be estimated using both geothermometric data and CO₂ fluid density in CO₂ inclusions in the rocks. Typical precisions of density of CO₂ in CO₂ inclusions obtained by the Raman microspectroscopic densimetry (~0.01 g/cm³) and by the microthermometry (< 0.001 g/cm³) correspond to uncertainties in the depth origin of 2.4 km and < 1.7 km, respectively, at 1000 ± 50 °C. In case of the mantle under 750–1250 °C and 1 GPa, the CO₂ fluid has a density ranging from 1.06 g/cm³ to 1.21 g/cm³, which are well measured by the Raman microspectroscopic densimetry. Combination of both densimetries for CO₂ in mantle minerals elucidates the deep structure of the Earth. Copyright © 2012 John Wiley & Sons, Ltd.     

Topological superconductivity in bilayer Rashba system

We theoretically study a possible topological superconductivity in the interacting two layers of Rashba systems, which can be fabricated by the heterostructures of semiconductors and oxides. The hybridization, which induces the gap in the single particle dispersion, and the electron-electron interaction between the two layers leads to the novel phase diagram of the superconductivity. It is found that the topological superconductivity without breaking time-reversal symmetry is realized when (i) the Fermi energy is within the hybridization gap, and (ii) the interlayer interaction is repulsive, both of which can be satisfied in realistic systems. Edge channels are studied in a tight-binding model numerically, and the several predictions on experiments are also given.     

Regioselective C-H bond functionalizations of acridines using organozinc reagents

Despite the recent advance in C-H bond functionalization chemistry, the C-H bonds in the acridine ring system, which is an important scaffold in medicinal and material science, have met with limited success, due, in part, to the lack of activated C-H bonds adjacent to the ring nitrogen atom. Herein, several protocols that can effect the regioselective arylation and alkylation of acridines at the C-4 and C-9 positions are described.     

Ni(0)/NHC-catalyzed amination of N-heteroaryl methyl ethers through the cleavage of carbon‒oxygen bonds

Ni(0)/NHC-based catalyst system can promote the amination of N-heteroaryl methyl ethers via the cleavage of normally unreactive carbon–oxygen bonds. Electron-deficient N-heteroarenes including pyridine, quinoline, isoquinoline, and quinoxaline undergo amination to afford aminopyridine and related heteroarenes, which constitute an important class of compounds.     

Heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a heat exchanger

This paper describes heat and mass transfer characteristics of organic sorbent coated on heat transfer surface of a fin-tube heat exchanger. The experiments in which the moist air was passed into the heat exchanger coated with sorption material were conducted under various conditions of air flow rate (0.5–1.0 m/s) and the temperature of brine (14–20°C) that was the heat transfer fluid to cool the air flow in the dehumidifying process. It is found that the sorption rate of vapor is affected by the air flow rate and the brine temperature. Meanwhile, the attempt of clarifying the sorption mechanism is also conducted. Finally the average mass transfer coefficient of the organic sorbent coated on heat transfer surface of a fin-tube heat exchanger is non-dimensionalzed as a function of Reynolds number and non-dimensional temperature, and it is found that the effect of non-dimensional temperature on them is larger than Reynolds number .     

Copper‐Catalyzed Borylative Allyl–Allyl Coupling Reaction

Borylative allyl–allyl coupling using allenes, bis(pinacolato)diboron, and allyl phosphates has been developed in the presence of a copper catalyst bearing an N‐heterocyclic carbene ligand. The reaction affords boryl‐substituted 1,5‐diene derivatives in good to high yields with high regioselectivity and Z selectivity.     

Cationic Ring-Opening Polymerization of 1,3-Dehydroadamantanes

Ring-opening polymerizations of [3.3.1]propellane derivatives, 1,3-dehydroadamantane ( 1 ) and 5-butyl-1,3-dehydroadamantane ( 2 ), were carried out with CF₃SO₃H in CH₂Cl₂ at 0 °C for 6–42 h. The central σ-bonds in 1 and 2 were exclusively opened to afford novel poly([3.3.1]propellane)s, poly(1,3-adamantane)s, in 52–95% yields. The resulting poly( 2 ) possessing flexible butyl substituent was soluble in chloroform, THF, and 1,2-dichlorobenzene, and the degree of polymerization was estimated to be greater than 30, while the poly( 1 ) was hardly soluble in the common organic solvents. All aliphatic poly( 1 ) and poly( 2 ) showed high thermal stability, their 10% weight loss temperatures were 421 and 486 °C, respectively.     

Path integrals as analysis on path space by time slicing approximation

This is a survey of our papers [3, 4]. We give a fairly general class of functionals on a path space so that Feynman path integral has a mathematically rigorous meaning. More precisely, for any functional belonging to our class, the time slicing approximation of Feynman path integral converges uniformly on compact subsets of the configuration space. Our class of functionals is closed under addition, multiplication, translation, real linear transformation and functional differentiation. The invariance under translation and orthogonal transformation, the interchange of the order with Riemann-Stieltjes integrals and some limits, the semiclassical approximation, the integration by parts and the Taylor expansion formula with respect to functional differentiation, and the fundamental theorem of calculus hold in Feynman path integral. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and electronic properties of hexylthiophene-octaethylporphyrin derivatives (HTh-OEP) connected with diacetylene linkage: substituent effect on the electronic structure of the extended HTh-OEP conjugation system

Octaethylporphyrin (OEP) was combined with 2-substituted 3-hexylthiophenes (HTh) by diacetylene linkage to afford the highly extended conjugation system (HTh-OEP). Their absorption spectral properties were examined, proving that the electronic structure of OEP is affected by the more electron-withdrawing substituents through the diacetylene linkage more dramatically. The substituent effect on the HTh-OEP conjugation system is much outstanding, as compared with that on the corresponding benzene system (Bzn-OEP).