Photochemistry of N-acylimino-isoquinolinium and -quinolinium betaines

The photochemical behavior of N-acyliminoisoquinolinium and -quinolinium betaines has been investigated. In contrast to pyridinium betaines, the principal course of reaction is the 1,2-migration of N-acylamino groups. Substituent effects as well as solvent effects are observed. The results are rationalized in terms of diaziridine intermediates.     

On the miscibility gap in liquid bismuth-bismuth tribromide system

We have determined the location of the miscibility gap in liquid Bi-BiBr₃ system in the concentration-temperature, x?T, plane from the measurement of the electrical conductivity. The measurements have been done in the concentration range between 30.5 and 92.5 mol.% Bi and in the temperature range between 300 and 600°C. It is found that the temperature dependence of the conductivity of the mixture changes near the retrograde solubility region.     

Mono-N-amino salt of benzodiazines and naphthyridines

The mono-N-amino salts of 3-phenylcinnoline, phthalazine, 1-phenylphthalazine, 4-phenylquinazoline, 2-phenylquinoxaline, 1,5- and 1,8-naphthyridines are in high yields prepared by direct N-amination of the parent heterocycles with O-mesitylenesulfonylhydroxylamine. With the one expection of 3-phenylcinnoline, the site of N-amination was determined by mass and nmr spectral techniques. The results indicate that the N-amination occurs preferentially at the least sterically hindered nitrogen atom.     

Acid-catalyzed cyclizations of n-vinyl-α-sulfinylacetamides A novel synthetic approach to erythrinane

Under the Pummerer reaction conditions, N-(1-cyclohexenyl)-N-methyl-α-(methylsulfinyl)acetamide ($\text{7a}$) cyclized in a 5-endo trigonal fashion through the intermediary cation ($\text{8}$) to give the tetrahydro-4H-oxindole ($\text{10}$). The reaction was successively applied to a novel synthesis of erythrinane skeleton.     

Outside dislocations generated from phosphorus implanted silicon layers

The growth, movement and nature of outside dislocation, which propagate from heavily phosphorus (>10¹⁵ ions/cm²) implanted (111), (100), and (110) silicon layers into unimplanted outside regions by a compressive strain induced during 1100° C wet O₂ annealing, are investigated using transmission electron microscopy and x-ray diffraction topography. Outside dislocations are formed, mainly on (111) planes., by the glide motion of dislocation networks formed in implanted layers during early annealing. This results in dislocations extending into the unimplanted areas to different degrees, in the order of, from the largest to smallest, (111), (110), and (100) wafers. In (110) wafers, the [001] oriented dislocations in the implanted regions rise to the surface at the implant and unimplant boundary. On the other hand, the [110] dislocations penetrate into the unimplanted region. Two sets of orthogonal 〈110〉 oriented dislocations generated in (100) implanted wafers behave in the same manner as the [001] dislocations in (110) wafers. Some sources of the compressive strain related to the generation of these dislocations are discussed.     

Spontaneous racemization and epimerization behavior in solution of chiral nitroxides

[reaction: see text] Enantiomerically enriched samples of chiral cyclic nitroxides with a 4-hydroxyphenyl group on the stereogenic center bearing the NO radical group undergo unprecedented spontaneous racemization and/or epimerization in aprotic solvents, which can be well accounted for by the multistep equilibrations involving planar quinoid intermediates.     

Experimental evidence for the p-d hybridization in the Cd-Ca quasicrystal: origin of the pseudogap

Ca 2p-3d resonant photoemission spectroscopy of a Cd6Ca crystalline approximant unambiguously demonstrates that the low-lying unoccupied 3d levels of calcium are lowered below the Fermi energy by the formation of the approximant, as suggested from electronic structure calculations [Phys. Rev. Lett. 87, 206408 (2001)]]. Moreover, the Ca 3d partial density of states (DOS) obtained near the Fermi energy is in reasonable agreement with theoretical Ca 3d DOS. These results verify the unconventional picture that the origin of the pseudogap in the Cd-based quasicrystals is due to hybridization of the Ca 3d band with the Cd 5p band.     

AND/OR bimolecular recognition

cis-Decalin (2) and perylene (3) are co-enclathrated by a self-assembled M6L4-coordination cage (1) to give 1 superset(2.3) although each of them is not enclathrated. This phenomenon is termed as AND bimolecular recognition because enclathration occurs only if 2 and 3 coexist. Cage 1 also coenclathrates azulene (8) and 1,4-naphthoquinone (9) to give 1 superset(8.9). In this case, 1 superset(8)2 and 1 superset(9)2 are formed by treating 1 with 8 and 9 individually. This case is termed as OR bimolecular recognition because enclathration occurs if 8 or 9 exists. Accordingly, we have shown that the self-assembled cage 1 experiences both AND and OR bimolecular recognition.     

NMR and MO Studies on the Molecular Structure of a Fluoranthene-Benzene Complex

Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The ¹H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the ¹H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of C_S symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the ¹H NMR spectral shifts mentioned above and the experimentally predicted C_S structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure.