Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane

The reductive coupling reaction of 1,4-bis(3-acetyl-5-tert-butyl-2-methoxyphenyl)butane 3 was carried out using TiCl₄-Zn in pyridine followed by a McMurry coupling reaction to afford the compounds anti and syn 1,2-dimethyl[2.4]MCP-1-ene 4. Bromination of 4 with BTMA-Br₃ in dry CH₂Cl₂ afforded the interesting compound 1,2-bis-(bromomethyl)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-1-ene 6 and consecutive debromination with Zn and AcOH in CH₂Cl₂ solution afforded the stable solid 5,15-di-tert-butyl-8,18-dimethoxy-1,2-dimethylene[2.4]MCP 7 in 89% yield. Compound 7 was conveniently employed in a Diels–Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to provide 2-(3′,6′-dihydrobenzo)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-4′,5′-dimethylcarboxylate 8 in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged compound [2.4]MCP 9 by aromatization. The chirality of the two conformers was characterized by circular dichroism (CD) spectra of the separated enantiomer which are perfect mirror images of each other.     

Transmission electron microscopy study of an AlN nucleation layer for the growth of GaN on a 7-degree off-oriented (0 0 1) Si substrate by metalorganic vapor phase epitaxy

We have investigated the morphology of the high-temperature-grown AlN nucleation layer and its role in the early stage of GaN growth, by means of transmission electron microscopy. The nitride was selectively grown on a 7-degree off-oriented (0 0 1) patterned Si substrate by metalorganic vapor phase epitaxy. AlN was deposited on the inclined unmasked (1 1 1) facet in the form of islands. The size of the islands varied along the slope, which is attributable to the diffusion of the growth species in the vapor phase. The GaN nucleation occurred at the region where rounded AlN islands formed densely. The threading dislocations were observed to generate in the GaN nucleated region.     

Transmission electron microscopy observation of GaAs/Al0.3Ga0.7As T-shaped quantum well structure fabricated by glancing angle molecular beam epitaxy on GaAs(100) reverse-mesa etched substrates

GaAs/Al_0.3Ga_0.7As multi-layer structures were grown on GaAs (100) reverse-mesa etched substrates by glancing angle molecular beam epitaxy (GA-MBE). A(111)B facet was formed as a side-facet. Surface migration of Ga and Al atoms from the (100) flat region to the (111)B side-facet region has been investigated to fabricate T-shaped GaAs/AlGaAs quantum wells (QWs) under the condition that Ga and Al atoms impinge only an the (100) flat region and do not impinge on the (111)B side-facet. Observation of T-shaped GaAs/AlGaAs quantum wires (QWRs) by cross-sectional transmission electron microscopy (TEM) revealed that there is no migration of Al atoms from the (100) to the (111)B facet region at a substrate temperature (T_s) as high as 630°C, under a V/III ratio of 28 (in pressure ratio). On the other hand, very thin GaAs epitaxial layers grown on the (111)B side-facet region owing to the Ga migration were observed for substrate temperatures of 600 and 630°C. It was found that the mass flow of Ga atoms from the (100) region to the (111)B side-facet region increases, with the thermal activation energy of 2.0 eV, as the substrate temperature increases from 570 to 630°C. The GA-MBE growth on a reverse-mesa etched GaAs substrate at a low temperature 570°C or lower is desirable to fabricate a nm-scale GaAs/AlGaAs QWR structure with nm-scale precision.     

Electrical transport in n-type semiconducting Ge120BixSe70−xTe10 glasses

Resistivity and thermoelectric power were measured as a function of temperature and composition for Ge₂₀Bi_xSe_70?xTe₁₀ glasses (x = 0–11). The results were compared with the case of of Ge₂₀Bi_xSe_80?x glasses to see on the electrical properties the influence of the substitution of Te for a part of Se. The glasses show n-type conduction for x ? 9, which was not affected by the substitution of Te. The resistivity was about three orders of magnitude lower for the glasses with x < 10, and remained almost the same for x ? 10, compared with the glasses not containing Te. From the composition dependence of the calculated concentration of covalent bonds in the glasses, it was proposed that the appearance of n-type conduction was closely related to the formation of a sufficient number of BiSe bonds and the disappearance of the bonds between two chalcogen atoms such as TeSe or SeSe bonds, and that the remarkably low resistivity in the present glasses with x < 10 was likely to be attributed to the formation of TeSe bonds.     

Base-mediated cyclization reaction of 2-alkynylphenylphosphine oxides: synthesis and photophysical properties of benzo[b]phosphole oxides

The base-mediated intramolecular cyclization reaction of 2-alkynylphenylphosphine oxides affords benzo[ b]phosphole oxides, which show intense blue-green fluorescence. Benzo[ b]phospholes are also prepared by the reduction of benzo[ b]phosphole oxides.     

Direct construction of bicyclic heterocycles by palladium-catalyzed domino cyclization of propargyl bromides

The palladium-catalyzed domino cyclization of propargyl bromides having two nucleophilic functional groups is described. Treatment of 1,7-diamino-5-bromohept-3-yne derivatives with catalytic Pd(PPh3)4 in the presence of NaH in MeOH gives the 2,7-diazabicyclo[4.3.0]non-5-enes in good yields. Interestingly, the regioselectivity of the reaction is completely controlled by the relative reactivity of the amine functional groups, irrespective of the position of the nucleophiles. The malonate derivative also undergoes domino cyclization to produce a hexahydroindole derivative.     

Tetrahedral Oligothiophenes; Synthesis,X‐ray Analysis,and Optoelectronic Properties of Highly Symmetrical, 3D‐Branched Oligothiophenes

Tetrakis(bithienyl)methane and tetrakis(terthienyl)methane have been synthesized from tetrakis(2‐thienyl)methane by use of Suzuki–Miyaura coupling as a key reaction. Their trimethylsilyl (TMS) derivatives are also synthesized. X‐ray analysis reveals that each oligothiophene moiety tends to adopt anti‐conformations and show relatively small torsion angles between the adjacent thiophene rings. While the longest absorption maxima of these tetrakis(oligothienyl)methanes exhibit only a slight bathochromic shift compared to the corresponding linear oligothiophene derivative, tetrakis(bithienyl)methane and its TMS derivative exhibit an appreciable red‐shift in their fluorescence spectra. The intramolecular interaction between thienyl groups of tetrakis(2‐thienyl)methane is supported by DFT calculation.     

Invisible photochromism of diarylethene derivatives

Diarylethene derivatives with oxidized thiophene rings shift their absorption band to a shorter wavelength in the UV region upon photocyclization; no color change was observed during the photochromic reaction, and the invisible photochromism is advantageous for devices used under room light.     

Palladium-catalysed biscyclisation of allenic bromoalkenes through a zipper-mode cascade

Treatment of allenic bromoalkenes bearing a nucleophilic moiety with a catalytic amount of palladium(0) in the presence of TBAF or Cs(2)CO(3) in MeCN affords bicyclic heterocycles in good to high yields, through zipper-mode cascade cyclisation.