An atropisomeric M2L4 cage mixture displaying guest-induced convergence and strong guest emission in water

Introduction of atropisomeric axes into a bent bispyridine ligand leads to the quantitative formation of a complex mixture of atropisomeric M₂L₄ cages upon treatment with metal ions. Whereas the isomer ratio of the obtained cage mixture, consisting of up to 42 isomers, is insensitive to temperature and solvent, the quantitative convergence from the mixture to a single isomer is accomplished upon encapsulation of a large spherical guest, namely fullerene C₆₀. The observed isomerization with other guests depends largely on their size and shape (e.g., <10 and 82% convergence with planar triphenylene and bowl-shaped corannulene guests, respectively). Besides the unusual guest-induced convergence, the present cage mixture displays the strongest guest emission (Φ_F = 68%) among previously reported M_nL_m cages and capsules, upon encapsulation of a BODIPY dye in water.

A complex mixture of atropisomeric M₂L₄ cages is shown to undergo perfect convergence to a single isomer upon encapsulation of spherical C₆₀ in water. Moreover, the cage mixture displays very strong guest emission upon encapsulation of a BODIPY dye.     

Conductive characteristics of radical‐bearing polythiophenes using a microcomb‐shaped electrode

The electric conductivity of π‐conjugated and radical‐bearing polymers, i.e., polythiophenes bearing pendant galvinoxyl and phenoxyl radical groups, was measured using a microcomb‐shaped electrode. The electric conductivity was found to be enhanced by the radical content in the polymer. The infrared (IR) and Raman spectroscopies suggested a structural change from an aromatic form to a quinoid one in the polythiophene backbone by the phenoxyl radical generation. The effect of the pendant galvinoxyl radical's unpaired electron on the electric conductivity of the polythiophene was discussed by comparing the conductivity of a radical‐bearing polystyrene and a polythiophene mixed with low‐molecular radical molecules. Copyright © 2007 John Wiley & Sons, Ltd.     

ZINC TETRAPHENYLPORPHYRIN-SENSITIZED PHOTOREDUCTION OF ANTHRAQUINONESULFONATE IN AQUEOUS MICELLAR SOLUTIONS*

Abstract— Zn-tetraphenylporphyrin (ZnTPP), solubilized in non-ionic surfactant micelles, was found to sensitize photoreductions of some sodium anthraquinonesulfonatesz in the presence of ascorbic acid under anaerobic conditions. The reaction rate was increased by the addition of an anionic surfactant, while retardation was observed with a cationic surfactant. The pH-reaction rate profiles showed maxima located in the order corresponding to pK_a-values for the semiquinone of each anthraquinone-sulfonate. A reaction scheme involving the formation of ZnTPP⁺ at the primary step, followed by back-reduction with ascorbic acid, is proposed. The reaction scheme is in good agreement with the results of flash photolysis. The surfactant micelles are suggested to aid the charge-separation between the ionic species just after the redox reaction involving the photoexcited ZnTPP and anthraquinonesulfonates.     

Variable Lebesgue norm estimates for BMO functions. II

The paper concerns characterization of BMO in terms of Banach function spaces. In particular, we are interested in characterizing BMO by using the variable Lebesgue norm.     

Discrimination of the geometrical isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines based on 1 H?Nmr spectral data

¹ H-Nmr spectra of cis and trans isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines were taken at various temperatures. The spectra of geometrical isomers bearing the ae or ea dimethyl groups showed broadening at lower temperatures. It was clarified that the measurement of the spectra at lower temperatures is useful for the discrimination of the geometrical isomers of dimethylpiperazines.     

Softening of Cu-O bond stretching phonons in tetragonal HgBa2CuO4+delta

Phonons in nearly optimally doped HgBa(2)CuO(4+delta) were studied by inelastic x-ray scattering. The dispersion of the low-energy modes is well described by a shell model, while the Cu-O bond stretching mode at high energy shows strong softening towards the zone boundary, which deviates strongly from the model. This seems to be common in the hole-doped high-T(c) superconducting cuprates, and, based on this work, not related to a lattice distortion specific to each material.     

Preparation and structures of novel silamacrocyclic compounds: silacalix[4]quinone and silacalix[4]hydroquinone octamethyl ether

X-ray crystallographic analysis revealed that novel silamacrocyclic compounds, 2,8,14,20-tetrasilacalix[4]quinone and 2,8,14,20-tetrasilacalix[4]hydroquinone octamethyl ether, adopted 1,3-alternate structures in the solid state.