Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Fracture mechanism of liquid‐crystalline epoxy resin systems with different phase structures

A liquid‐crystalline epoxy resin was cured at two different temperatures. The phases of the cured systems clearly showed isotropic and nematic polydomain structures, which depended on the curing temperature. The fracture toughness of the systems was measured, and the fracture mechanism was investigated with polarized IR measurements. The nematic polydomain structure system showed considerably higher fracture toughness than the isotropic structure. Moreover, both systems exhibited a reorientation of the network chains near the fracture surface during the fracture process, and the region of the network reorientation in the nematic polydomain structure system was larger than that in the isotropic structure system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4044–4052, 2004     

Optical properties of impurity atoms in pressurized superfluid helium

We report on the optical properties of alkali atoms (Cs and Rb) in the pressurized superfluid helium. We observed excitation and emission spectra at various pressures from the saturated vapor pressure to about 25 atm. The theoretical calculations on the basis of the atomic bubble model have also been worked out. The qualitative agreement between the theoretical and experimental results with respect to the peak shift, the linewidth, and their pressure dependence is achieved in the framework of the spherical atomic bubble model. TheD ₂ excitation spectra with the double peaks are interpreted qualitatively in terms of the Jahn-Teller effect, indicating the existence of the nontotally symmetrical density distribution of the surrounding helium atoms.     

Effect of plasma treatment on interface property of BCN/GaN structure

Interface properties of BCN/GaN metal-insulator-semiconductor (MIS) structures are investigated by X-ray photoelectron spectroscopy (XPS) and capacitance versus voltage (C-V) characteristics measurements. The BCN/GaN samples are fabricated by in situ process consisting of plasma treatment and deposition of BCN film in the plasma-assisted chemical vapor deposition (PACVD) apparatus. XPS measurement shows that the oxide formation at the BCN/GaN interface is suppressed by nitrogen (N₂) and hydrogen (H₂) plasma treatment. The interface state density is estimated from C-V characteristics measured at 1 MHz using Terman method. The minimum interface state density appears from 0.2 to 0.7 eV below the conduction band edge of GaN. The minimum value of the interface state density is estimated to be 3.0 × 10¹⁰ eV⁻¹ cm⁻² for the BCN/GaN structure with mixed N₂ and H₂ plasma treatment for 25 min. Even after annealing at 430 °C for 10 min, the interface state density as low as 6.0 × 10¹⁰ eV⁻¹ cm⁻² is maintained.     

Precise measurement of magnetic moment of short-lived β-emitting nuclei12B ( I π=1+, T 1/2=20.18 ms)

The spin polarized β-emitting nuclei¹²B (I ^π=1⁺,T _1/2=20.18 ms) were produced by the nuclear reaction¹¹B(d, p)¹²B and by the selection technique of the incident deuteron energy and the¹²B recoil angle following the nuclear reaction. The nuclear magnetic moment of the short-lived nuclei¹²B was measured by β-NMR with the β-NMR and β-NQR setup established for the first time in China. The nuclear magnetic moment of¹²B was determined to be μ=0.99993±0.00048 nm org=0.99993±0.00048 after the precise correction of the Knight shift.     

Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators

A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB₈ 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB₈ 9‐miktoarm star copolymers were cleaved by treating with Me₃SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007.     

Decomposition mechanism of triethylindium (TEI) on a GaP(0 0 1)-(2×1) surface studied by LEED, AES, TPD and HREELS

Adsorption and decomposition of triethylindium (TEI: (C₂H₅)₃In) on a GaP(0 0 1)-(2×1) surface have been studied by low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). It is found from the TPD result that ethyl radical and ethylene are evolved at about 300–400 and 450–550 K, respectively, as decomposition products of TEI on the surface. This result is quite different from that on the GaP(0 0 1)-(2×4) surface. The activation energy of desorption of ethyl radical is estimated to be about 93 kJ/mol. It is suggested that TEI is adsorbed molecularly on the surface at 100 K and that some of TEI molecules are dissociated into C₂H₅ to form P–C₂H₅ bonds at 300 K. The vibration modes related to ethyl group are decreased in intensity at about 300–400 and 450–550 K, which is consistent with the TPD result. The TEI molecules (including mono- and di-ethylindium) are not evolved from the surface. Based on the TPD and HREELS results, the decomposition mechanism of TEI on the GaP(0 0 1)-(2×1) surface is discussed and compared with that on the (2×4) surface.     

A SAXS study of the nanometer scale hybrid structure of Si---Ti---C---O amorphous fibers

A small-angle X-ray scattering (SAXS) study was performed to reveal the nanometer scale hybrid structure of Si---Ti---C---O fibers prepared by the pyrolysis of polytitanocarbosilane. The SAXS profile for Si---Ti---C---O fibers is attributed to two different types of scattering entities: an anisotropic contribution from long filaments with diameters hundreds to thousands of Ångströms and an isotropic contribution from β-SiC fine clusters of about a nanometer in diameter. A drastic degradation in the tensile strength of the fibers is correlated to the characteristic variations in their long-and medium-range structure.