D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

A perfect one-factorization ofK 36

In this paper, a perfect one-factorization ofK ₃₆ is given, which is factor-1-rotational.     

Accelerated glycosylation under frozen conditions

O-Glycosylations using thiomethyl glycosides as donors were compared under both frozen and unfrozen conditions. In the presence of MeOTf as a promoter, enormous rate acceleration was observed when the glycosylation was conducted in p-xylene below its freezing point.     

Thermolysis of reactive oligo(p-phenylene sulfide) containing disulfide bond

Oligo(phenylene sulfide) (OPS) containing one disulfide bond at the end of the chain, which was obtained by the oxidative polymerization of diphenyl disulfide, had a relatively low Td_10%(temperature for 10% weight loss) of 412 °C because of degradation of the disulfide bond. But this thermal cleavage of the disulfide bond promoted the curing reaction through thiophenoxy radical formation. OPS was allowed to react with diiodobenzene at 220 °C. The thermal stability of OPS was improved through the consumption of the disulfide bond and the coupling of the chain.     

Fluorescence modification of Gb3 oligosaccharide and rapid synthesis of oligosaccharide moieties using fluorous protective group

The use of the bisfluorous chain-type propanoyl (Bfp) group as a fluorous protective group made it possible to rapidly synthesize the Gb2 and Gb3 oligosaccharide derivatives by a simple fluorous-organic extraction purification. Furthermore, the fluorescence-labeled Gb2 and Gb3 oligosaccharides were prepared as a potential Vero Toxins detecting reagent.     

Stability of porphyrin-calix[4]arene complexes analyzed by electrospray ionization mass spectrometry

The stability of some porphyrin-calix[4]arene sodium-ion complexes were determined by a collision-activated decomposition (CAD) method utilizing electrospray ionization mass spectrometry (ESI-MS). Comparing the values of E(1/2), the collision energy at which the relative intensity of the complex ion is 0.5, we found that the porphyrin-calix[4]arene complex with the higher value of E(1/2) corresponded to that with the larger association constant (Kass), as measured by 1H-NMR in CDCl3. Both our ESI-MS and NMR studies proved that the number of hydrogen bonds and the rigidity of the calix[4]arene stabilized the complex. The ESI-MS technique could be successful in screening the binding affinity in host-guest systems with a small amount of sample.     

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.     

Development of Odorless Thiols and Sulfides and Their Applications to Organic Synthesis

Summary. Development of new odorless thiols (dodecanethiol, 4-n-heptylphenylmethanethiol, 4-trimethylsilylphenylmethanethiol, 4-trimethylsilylbenzenethiol) and an odorless sulfide (1-methylsulfanyldodecane) and their applications to dealkylation, Michael addition, Swern oxidation, and Corey-Kim oxidation are described.     

Synthesis of poly(2,5-dimethylphenylene sulfide) through oxidative polymerization of sulfur chloride with p-xylene

Poly(2,5-dimethylphenylene sulfide) was prepared by oxidative polymerization of sulfur chloride with p-xylene using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as an oxidizing agent. The reaction proceeded efficiently under atmospheric pressure and at room temperature. The polymer formed had a high melting temperature and linear structure which was confirmed by spectroscopies. The effects of reaction time, solvent, temperature and oxidizing agent on polymerization are also discussed.     

Dynamical property of YFeMnO4

In order to interpret abrupt changes of distributions of orientations andmagnitudes of hyperfine fields in Mössbauer measurements of⁵⁷Fe in YFeMnO₄, a model is proposed. The origin is assumed to be not static but dynamic. Fluctuating fields are caused by spins in a fully frustrated spin system, namely, a Heisenberg spin system on a triangular lattice in a two-dimensional antiferromagnet. Extending the stochastic theory for the fluctuation between two states to that among many states with a Gaussian distribution, we fit the spectra with three parameters, hyperfine fieldH _hf, correlation time _c, andwidth of fluctuating field , within a limited condition of =_c=1. Obtained results represent the characteristic features of Mössbauer spectra well, in spite of a simplified model.