Synthesis and characterization of 9,9‐bis(4‐hydroxyphenyl and 4‐aminophenyl)dibenzofluorenes: Novel fluorene‐based monomers

Two novel 9,9‐difunctionalized fluorene‐type monomers, 9,9‐bis(4‐hydroxyphenyl‐ and 4‐aminophenyl)‐2,3:6,7‐dibenzofluorenes, are synthesized by the reaction of dibenzenzofluorenone with phenol and aniline. These monomers are used for the preparation of polyester and polyimide as the typical polymers to evaluate the property change such as thermal stability caused by the benzene rings fused to the fluorene skeleton with keeping good solubility, in comparison with the polymers derived from simple fluorenone. In fact, these two new polymers have the fairly enhanced thermal stability and refractive index value along with satisfactory solubility in organic solvents, enough to emphasize the fusion effect. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2602–2605     

Diffusion of hydrogen in metals

The present status of our understanding of the diffusion of hydrogen in metals, both experimental and theoretical, is reviewed. Discussions are focused on the mechanism of diffusion of hydrogen isotopes H, D and T in f.c.c. and b.c.c. metals; the positive muon (μ ⁺) is referred to where appropriate. An up-to-date compilation of diffusion data as a function of temperature and isotope mass has been made, and a clear distinction in general diffusion behaviour in f.c.c. and b.c.c. metals is noted. Subsequently, the results obtained from the Gorsky effect, nuclear magnetic resonance and quasi-elastic neutron scattering that provide information on elementary jump processes are discussed.

A conceptual framework of the quantum diffusion of light interstitials in metals is given, including the recent Kondo theory that emphasizes the crucial importance of particle-conduction electron interactions in the diffusion process, especially at low temperatures. It is shown with the help of recent estimates of the tunneling matrix element that the overall feature of diffusion of hydrogen isotopes in b.c.c. metals as well as μ ⁺ in f.c.c. metals can be explained consistently within the frame presented here.

Finally, recent advances in the diffusion studies on hydrogen in b.c.c. metals are described. They include a re-analysis of quench-recovery experiments that manifested nearly athermal diffusion of H, D and T in Ta at low temperatures, and an enormous enhancement of the diffusivity under stress (superdiffusion) observed for H and D in V.     

Detailed Analysis of the Crystal Structures and Magnetic Properties of a Dysprosium(III) Phthalocyaninato Sextuple-Decker Complex: Weak f–f Interactions Suppress Magnetic Relaxation

In the research field of single-molecule magnets (SMMs), lanthanoid–lanthanoid interactions, so-called f–f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f–f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the Dy^III-Cd^II-phthalocyaninato sextuple-decker complex (Dy₂Cd₃) reveals that the intramolecular Dy−Dy length in Dy₂Cd₃ is more than 13 Å, which is longer than the intermolecular Dy−Dy length. Even though the two Dy^III ions are far apart, intermolecular ferromagnetic dipole–dipole interactions are observed in Dy₂Cd₃. From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy₂Cd₃ is partially suppressed owing to the existence of very weak Dy−Dy interactions. Our results show that even very weak Dy−Dy interactions act as a dipolar bias, suppressing QTM.     

Aryl-β-C-glucosidation using glucal boronate: application to the synthesis of tri-O-methylnorbergenin

Novel aryl-β-C-glucosidation method using glucal boronate was developed. This protocol can offer several advantages including use of non-toxic, easily handling glucal boronate as a crystalline solid and storable at room temperature for several months. Tri-O-methylnorbergenin (8,10-di-O-methylbergenin), an anti-HIV active bergenin derivative, was concisely synthesized by application of the aryl-β-C-glucosidation method.     

Complexation of acyclic ligands having two terminal quinoline units with alkali metal cations

Abstract

Acyclic multidentate ligands consisting of an oligooxyethylene chain (di-, tri-, tetra-, and penta-) and two terminal rigid quinaldate end groups were newly prepared and their complexation properties with alkali metal cations were estimated by the solvent extraction method to indicate a better affinity for K⁺. Among them, the tetraethylene glycol derivative showed the highest K⁺ binding on about the same level as 18-crown-6. Their conformations in solution and in the solid state were examined by using ¹H- and ¹³C-NMR spectroscopy and X-ray crystal analyses, respectively. The better binding of K⁺ in comparison with the corresponding glymes or analogues having the same donor sites was reasonably explained by considering the effective co-ordination of the carbonyl oxygen of the ester groups and the parallel π-stacking interaction between two quinaldate surfaces.     

pH-Responsive Phase Transition of Supramolecular Hydrogel Consisting of Glycosylated Amino Acetate and Carboxylic Acid Derivative

By addition of a carboxylated amino acetate (2) to a low-molecular-weight hydrogel (1) which has a unique thermally induced volume-phase transition character, a macroscopic pH-responsive feature is newly conferred on the supramolecular hydrogel. The direct observation of temperature-dependent behavior of the mixed hydrogel clearly showed that the thermally induced swelling-shrinkage type of the volume phase transition at pH 4 is shifted to the gel–sol transition at pH 7 by 10?mol% addition of 2 to the hydrogel 1. On the basis of the measurements by TEM, SEM, XRD and FT-IR, it is conceivable that incorporation of the anionic carboxylate of 2 slightly disturbs the packing of the hydrogen bond belt of the mixed hydrogel. Such a slight disturbance greatly leads to the sol–gel transition by elevating temperature, instead of the volume-phase transition. Introduction of dynamic characteristics to supramolecular systems in a macroscopic level may extend the potential of these materials in various fields.     

Thermal behavior and dismantlability of adhesives containing various inorganic salts

As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts.