Unprecedented diastereoselective generation of chiral-at-metal, half sandwich Ir(III) and Rh(III) complexes via anomeric isomerism on "sugar-coated" N-heterocyclic carbene ligands

The first example of the diastereoselective synthesis induced by anomeric isomerism of sugar units in ligands of metal complexes was demonstrated. S and R configurations of chiral-at-metal Ir(III) and Rh(III) complexes were selectively obtained by using chelate-type NHC ligands with α- and β-glucopyranosyl units, respectively.     

Incorporation of cationic electron donor of Ni-pyridyltetrathiafulvalene with anionic electron acceptor of polyoxometalate

A new salt-[Ni(II)(DMSO)(5)(TTFPy)](2)[α-SiW(12)O(40)] (1)-based on polyoxometalates was prepared by coordinating a cationic electron donor of pyridyltetrathiafulvalene (TTFPy) with Ni(II). Although the TTFPy molecule did not form a salt with the anionic α-[SiW(VI)(12)O(40)](4-) because of the weak charge-transfer (CT) interaction, the coordination of Ni with the pyridyl moiety permitted salt formation driven by electrostatic interaction, giving a single crystal of 1. Crystallographic analysis, UV-vis and IR spectroscopy and electrochemical characterization revealed that the fully oxidized α-[SiW(VI)(12)O(40)](4-) was crystallized with the neutral TTFPy moiety from the acetonitrile solution because of the low electron-withdrawing ability of α-[SiW(VI)(12)O(40)](4-), forming a brown-orange crystal. The crystal colour quickly turned to black by immersing in methanol, due to CT from TTF moiety to α-[SiW(VI)(12)O(40)](4-), which was caused by the solvent effect. Increase in the solvent acceptor number from 18.9 for acetonitrile to 41.3 for methanol resulted in the enhancement of the electron withdrawing ability of α-[SiW(VI)(12)O(40)](4-) by 0.317 V in methanol.     

Algebraic Independence of Solutions of First-Order Rational Difference Equations

We prove a theorem on algebraic independence of solutions of first order rational difference equations. By the theorem, we are able to prove algebraic independence of x, the exponential function e ^x and the Weierstrass function ${\wp(x)}$ over ${\mathbb{C}}$ only by seeing degrees of polynomials associated with their double angle formulas. As a corollary, we obtain a result on unsolvability of a first-order rational difference equation by solutions of other first-order rational difference equations, which implies its irreducibility. Additionally, we introduce some applications to algebraic independence of functions f(x), f(x ²), . . . , f(x ⁿ ).     

Efficient Nonlinear Optical Properties of Dyes Confined in Interlayer Nanospaces of Clay Minerals

Nonlinear optical (NLO) responses from organic dyes can be maximized when the dyes are aligned in appropriate manners in bulk materials. The use of restricted nanospaces provided by interlayer spacing of inorganic layered materials is a promising strategy for imposing suitable molecular alignments for NLO materials on dyes. The hybrid materials thus obtained exhibit salient NLO responses owing to the improved molecular orientation. In some cases, extension of the π‐electron system as a consequence of improved molecular planarity, obtained by the intercalation of a dye into the 2‐dimensional interlayer space of an inorganic layered material, is also observed as a factor that enhances NLO responses of chromophores at the molecular level. This review focuses on recent progress in the strategies for controlling the molecular orientation of NLO‐phores by employing clay minerals, which are one of the typical inorganic layered materials. In addition, development of a means for fabricating composites that satisfy the properties of an optical material, such as a sufficient size and thickness, a flat surface, and low light‐scattering characteristics is required to utilize the superior NLO properties observed for clay/dye hybrid materials for practical applications. A novel means for obtaining such a hybrid material is also outlined.     

Investigation of the photovoltaic performance of the polycrystalline silicon p–n junction by a photothermal measurement

For establishing a new methodology for evaluating an effect of the grain boundaries, both the piezoelectric photo-thermal (PPT) and the surface photo-voltage (SPV) measurements of polycrystalline Si p–n junction samples with different volume fractions of grain boundaries were carried out. We could define the signal intensity ratio of SPV/PPT as the key indicator of photovoltaic performance. This is because the PPT signal implies the phonon emitting carrier loss, whereas the SPV denotes the photo-excited carrier accumulation at the surface and the junction interface. It was found that the SPV/PPT ratio and solar cell efficiency decreased with increasing volume fraction of the grain boundaries. Present experimental results demonstrated that one can directly estimate the photovoltaic performance of in-process polycrystalline Si p–n junction wafer by adopting the combination of the PPT and the SPV methodologies without electrodes. Since the PPT detects the non-radiative recombination process, present methodology and the laser-beam-induced current and the photoluminescence imaging methods are complementary. By complementary use of these methods, it becomes possible to investigate the characteristic of grain boundary.     

Transmission coefficients in the presence of multistep-direct reactions

Formal expressions for transmission coefficients governing the multistep-compound process and introduced in an earlier paper, are explicitly worked out, using the idea of a multistep-direct process populating the compound nucleus. A perturbative treatment of inelastic scattering, combined with a “never come back” and the sudden approximation, and a statistical average over exit channels lead to simple, intuitively appealing expressions which contain shell-model type matrix elements and partial level densities and are therefore amenable to numerical evaluation.     

Adsorption/desorption of water on glass fiber surfaces

The interaction of water with glasses and ceramics has a profound effect on their properties. For many samples, standard analytical techniques are inappropriate or insufficiently sensitive for the detection of associated water. A thermodesorption method with an electrolytic detector is described which permits the measurement of minute quantities of water associated with such samples. Because of the sensitivity of the method, the surface water present on low specific area substrates can be measured. A simple and rapid method for obtaining water adsorption isotherms at low pressures is described. A preliminary investigation of single mode optical fibers demonstrates their substantial adsorptive capacity for water, due to the cladding used. Adsorbed water is also shown to differ on two glasses of similar bulk composition, presumably due to large differences in glass surface composition.