Circularly Polarized Luminescence in Supramolecular Assemblies of Chiral Bichromophoric Perylene Bisimides

Chiral bichromophoric perylene bisimides are demonstrated as active materials of circularly polarized emission. The bichromophoric system exhibited circularly polarized luminescence with dissymmetry factors typical of that of similar organic chiral chromophoric systems in the monomeric state. Variation in solvent composition led to the formation of stably soluble helical aggregates through intermolecular interactions. A large enhancement in the dissymmetry of circularly polarized luminescence was exhibited by the aggregated structures both in the solution and solid states. The sum of excitonic couplings between the individual chromophoric units in the self‐assembled state results in relatively large dissymmetry in the circularly polarized luminescence, thereby giving rise to enhanced dissymmetry factors for the aggregated structures. The spacer between chiral center and chromophoric units played a crucial role in the effective enhancement of chiroptical properties in the self‐assembled structures. These materials might provide opportunities for the design of a new class of functional bichromophoric organic nanoarchitectures that can find potential applications in the field of chiroptical memory and light‐emitting devices based on supramolecular electronics.     

Planar chirality of twisted trans-azobenzene structure induced by chiral transfer from binaphthyls

The absolute configuration of a binaphthyl-azobenzene dyad 2b, which has a chiral axis and a chiral plane, was determined by comparing the experimental circular dichroism (CD) spectra with the theoretical CD spectra calculated by the time-dependent (TD)-DFT method. The CD signals of the trans-azobenzene moiety indicated that the two benzene rings of this moiety are twisted unidirectionally. It is suggested that these dyads with shorter linkers may be suitable for use as chiroptical switches.     

Neutron induced light-ion production from iron and bismuth at 175 MeV

We have measured light-ion (p, d, t, ³He and α) production in the interaction of 175 MeV neutrons with iron and bismuth with low-energy thresholds and for a wide angular range (from 20° to 160°, in steps of 20°). Measurements have been performed with the Medley setup, semi-permanently installed at the The Svedberg Laboratory, Uppsala (Sweden), where a quasi-monoenergetic neutron beam is available and well characterized. Medley is a conventional spectrometer system and consists of eight telescopes, each of them composed of two silicon surface barrier detectors, to perform particle identification, and a CsI(Tl) scintillator to fully measure the kinetic energy of the produced light-ions. We report preliminary double-differential cross sections for production of protons, deuterons and tritons in comparison with model calculations using TALYS-1.0 code. These show better agreement for the production of protons, while the theoretical calculations seem to overestimate the experimental production of deuterons and tritons.     

Material characterization of superconducting T′-Nd2CuO4 films synthesized by metal organic decomposition

Recently we have achieved superconductivity in T′-RE₂CuO₄ (RE = Pr, Nd, Sm, Eu, and Gd), films by metal organic decomposition (MOD). In this article, we first report the cation off-stoichiometry effect, which aims at screening out the possibility of hole doping by cation deficiencies. We also investigated the structure and microstructure of superconducting T′-Nd₂CuO₄ films synthesized by MOD. This investigation aims at elucidating why MOD-grown Nd₂CuO₄ films become superconducting whereas our previous Nd₂CuO₄ films grown by molecular beam epitaxy were not superconducting.     

Convenient synthesis of 1,6,7,8-substituted 2-(3′,4′-substituted-phenyl)-4-quinolones via a 4-ethoxyflavylium salt

Condensation of 2-hydroxyacetophenone with benzaldehyde in the presence of 70% perchloric acid in ethyl orthoformate gave the corresponding 4-ethoxyflavylium perchlorate, which was treated with aqueous ammonia or methylamine solution to afford 1,6,7,8-substituted 2-(3′,4′-substituted-phenyl)-4-quinolone in fair to good yield.     

Novel Catalytic Hydrogenolysis of Trimethylsilyl Enol Ethers by the Use of an Acidic Ruthenium Dihydrogen Complex

The heterolytic cleavage of H ₂ is the key to the novel catalytic hydrogenolysis of trimethylsilyl enol ethers catalyzed by [RuCl(η²-H₂)(dppe)₂]OTf (dppe = 1,2-bis(diphenylphosphanyl)ethane, OTf = trifluoromethanesulfonate), which results in the formation of a ketone and Me₃SiH (see scheme). In addition, the stoichiometric, ruthenium-assisted protonation of a prochiral lithium enolate with H₂ gave a chiral ketone with high enantioselectivity (up to 75 % ee).     

Thermodynamic interactions in rubbery polymer/gas systems

The Flory–Huggins interaction parameters χ for 23 gases (He, Ne, Ar, Kr, Xe, H₂, N₂, O₂, N₂O, CO₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, 1,3-C₄H₆, four C₄H₈'s, n-C₄H₁₀, iso-C₄H₁₀, and n-C₅H₁₂) in five rubbery polymers (1,2-polybutadiene (PB), poly(ethylene-co-vinyl acetate)) (EVAc), polyethylene (PE), polypropylene (PP), and poly(dimethyl siloxane) (PDMS) were determined from either literature data on Henry's law coefficient and partial molar volume or those on sorptive dilation for each polymer/gas system. Values of χ for the gases increased in the order of PDMS < PP ≡ PB < EVAc ≡ PE. Among the gases except He and H₂ whose χ values are not reliable, Ne and Xe have respectively the highest and the lowest values of χ for the polyolefins. The χ values of the hydrocarbons were compared together with previously reported χ values of n-alkanes C₃-C₁₀. The dependencies of χ upon concentration and temperature were discussed on the basis of the literature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1049–1053, 1997     

Micropattern of GeO2/GeC lines prepared by UV irradiation and heat treatment of polygermane copolymers of methylphenylgermylene/phenylgermyne units

Upon ultraviolet irradiation of polygermane copolymers of methylphenylgermylene/phenylgermyne units (PhMeGe)_n(PhGe)_m in air, the germanium–germanium bond in the copolymer film changed into a digermoxane chain. Laser flash photolysis of the copolymer film showed the intermediacy of polygermyl radicals generated by Ge–Ge bond homolysis. The XPS showed the formation of germanium carbide (GeC) and germanium dioxide (GeO₂) upon heating the unirradiated and irradiated copolymer (PhMeGe)_n(PhGe)_m films, respectively. A relatively high-resolution micro- pattern of GeC/GeO₂ was obtained by combining the photochemical and thermal properties of the copolymers of methylphenylgermylene/phenylgermyne units. © 1997 John Wiley & Sons, Ltd.