A five‐coordinate iron(III) porphyrin complex including a neutral axial pyridine N‐oxide ligand

While six‐coordinate iron(III) porphyrin complexes with pyridine N‐oxides as axial ligands have been studied as they exhibit rare spin‐crossover behavior, studies of five‐coordinate iron(III) porphyrin complexes including neutral axial ligands are rare. A five‐coordinate pyridine N‐oxide–5,10,15,20‐tetraphenylporphyrinate–iron(III) complex, namely (pyridine N‐oxide‐κO)(5,10,15,20‐tetraphenylporphinato‐κ⁴N,N′,N′′,N′′′)iron(III) hexafluoroantimonate(V) dichloromethane disolvate, [Fe(C₄₄H₂₈N₄)(C₅H₅NO)][SbF₆]·2CH₂Cl₂, was isolated and its crystal structure determined in the space group P. The porphyrin core is moderately saddled and the Fe—O—N bond angle is 122.08 (13)°. The average Fe—N bond length is 2.03 Å and the Fe—ONC₅H₅ bond length is 1.9500 (14) Å. This complex provides a rare example of a five‐coordinate iron(III) porphyrin complex that is coordinated to a neutral organic ligand through an O‐monodentate binding mode.     

Computable analysis and Blaschke products

We show that if a Blaschke product defines a computable function, then it has a computable sequence of zeros in which the number of times each zero is repeated is its multiplicity. We then show that the converse is not true. We finally show that every computable, radial, interpolating sequence yields a computable Blaschke product.

     

$$L^2$$ L 2 Properties of Lévy Generators on Compact Riemannian Manifolds

Journal of Theoretical Probability - We consider isotropic Lévy processes on a compact Riemannian manifold, obtained from an $${\mathbb {R}}^d$$ -valued Lévy process through rolling...     

Hydrogenation of sp-bonded carbon surfaces using methane plasma

Highly ordered pyrolytic graphite was exposed to radio-frequency methane plasma to produce a hydrogen-terminated carbon surface. The effects of treatment parameters, namely exposure time, applied power and methane pressure, upon the treated surfaces’ chemical and morphological properties were systematically investigated. Scanning tunnelling microscopy measurements showed growth features on the plasma treated surface, the coverage of which was shown to increase with plasma exposure time or applied plasma power and decrease with gas pressure. Analyses of post-treated surface structures (via static secondary ion mass spectrometry with the aid of principle component analysis) showed an increase in surface hydrogen with plasma exposure time, applied plasma power and decreasing gas pressure. The results of these analyses were further supported by elastic recoil detection analysis measurements, which showed similar trends for the experimental parameters on the resultant surface hydrogen content.     

Synthesis, alignment, and magnetic properties of monodisperse nickel nanocubes

This Communication describes the synthesis of highly monodispersed 12 nm nickel nanocubes. The cubic shape was achieved by using trioctylphosphine and hexadecylamine surfactants under a reducing hydrogen atmosphere to favor thermodynamic growth and the stabilization of {100} facets. Varying the metal precursor to trioctylphosphine ratio was found to alter the nanoparticle size and shape from 5 nm spherical nanoparticles to 12 nm nanocubes. High-resolution transmission electron microscopy showed that the nanocubes are protected from further oxidation by a 1 nm NiO shell. Synchrotron-based X-ray diffraction techniques showed the nickel nanocubes order into [100] aligned arrays. Magnetic studies showed the nickel nanocubes have over 4 times enhancement in magnetic saturation compared to spherical superparamagnetic nickel nanoparticles.     

The dedicated high‐resolution grazing‐incidence X‐ray scattering beamline 8‐ID‐E at the Advanced Photon Source

As an increasingly important structural‐characterization technique, grazing‐incidence X‐ray scattering (GIXS) has found wide applications for in situ and real‐time studies of nanostructures and nanocomposites at surfaces and interfaces. A dedicated beamline has been designed, constructed and optimized at beamline 8‐ID‐E at the Advanced Photon Source for high‐resolution and coherent GIXS experiments. The effectiveness and applicability of the beamline and the scattering techniques have been demonstrated by a host of experiments including reflectivity, grazing‐incidence static and kinetic scattering, and coherent surface X‐ray photon correlation spectroscopy. The applicable systems that can be studied at 8‐ID‐E include liquid surfaces and nanostructured thin films.     

Size-dependent effects on electrical contacts to nanotubes and nanowires

Metal-semiconductor contacts play a key role in electronics. Here we show that for quasi-one-dimensional (Q1D) structures such as nanotubes and nanowires, side contact with the metal only leads to weak band realignment, in contrast with bulk metal-semiconductor contacts. Schottky barriers are much reduced compared with the bulk limit, and should facilitate the formation of good contacts. However, the conventional strategy of heavily doping the semiconductor to obtain Ohmic contacts breaks down as the nanowire diameter is reduced. The issue of Fermi level pinning is also discussed, and it is demonstrated that the unique density of states of Q1D structures makes them less sensitive to this effect. Our results agree with recent experimental work, and should apply to a broad range of Q1D materials.     

Relationship between structural and stress relaxation in a block-copolymer melt

The relationship between structural relaxation on molecular length scales and macroscopic stress relaxation was explored in a disordered block-copolymer melt. Experiments show that the structural relaxation time, measured by x-ray photon correlation spectroscopy is larger than the terminal stress relaxation time, measured by rheology, by factors as large as 100. We demonstrate that the structural relaxation data are dominated by the diffusion of intact micelles while the stress relaxation data are dominated by contributions due to disordered concentration fluctuations.     

An experimental and theoretical study of ring closing dynamics in HN3

We report on an H(D)-atom Rydberg tagging experiment for H(D)N(3) photolysis providing detailed dynamical information on the wavelength dependence of the H(D) + N(3) channel. We observe subtle yet striking changes in the photochemical dynamics as the photolysis energy passes through approximately 5.6 eV. In addition to producing linear azide with an average of approximately 40% of available energy appearing as translation, a second H(D)-atom producing channel grows in above this energy releasing only about 15%. An observed (inverse) isotope effect suggests that statistical decomposition on S(0) is unimportant. High level ab initio quantum chemical calculations reveal a transition state to cyclization of the N(3) moiety in H(D)N(3) on the first excited singlet (S(1)) surface that is close in energy to the experimentally observed threshold energy for this "slow channel". Furthermore, the translational energy release of the "slow channel" is energetically consistent with cyclic-N(3) formation. This work provides the clearest presently available insights into how ring closure can occur in azide photochemistry.     

Evaluation of initiator systems for controlled and sequentially curable free‐radical/cationic hybrid photopolymerizations

Free‐radical/cationic hybrid photopolymerizations of acrylates and epoxides were initiated using a three‐component initiator system comprised of camphorquinone as the photosensitizer, an amine as the electron donor, and a diaryliodonium salt. Thermodynamic considerations revealed that the oxidation potential of the electron donor must be less than 1.34 V relative to SCE for electron transfer with the photoexcited camphorquinone to take place. This electron transfer leads to the production of the active centers for the hybrid polymerization (two radicals and a cation). Further investigation revealed that only a subset of electron donors that meet the oxidation potential requirement resulted in polymerization of the epoxide monomer; therefore, a second requirement for the electron donor (pK_b higher than 8) was established. Experiments performed using a combination of electron donors revealed that the onset of the hybrid system's cationic polymerization can be advanced or delayed by controlling the concentration and composition of the electron donor(s). These studies demonstrate that a single three‐component initiator system can be used to initiate and chemically control the sequential curing properties of a free‐radical/cationic hybrid photopolymerization and is a viable alternative to separate photoinitiators for each type of polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1747–1756, 2005