Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Covariant Sectors with Infinite Dimension¶and Positivity of the Energy

Let ? be a local conformal net of von Neumann algebras on S ¹ and ρ a M?bius covariant representation of ?, possibly with infinite dimension. If ρ has finite index, ρ has automatically positive energy. If ρ has infinite index, we show the spectrum of the energy always to contain the positive real line, but, as seen by an example, it may contain negative values. We then consider nets with Haag duality on ℝ, or equivalently sectors with non-solitonic extension to the dual net; we give a criterion for irreducible sectors to have positive energy, namely this is the case iff there exists an unbounded M?bius covariant left inverse. As a consequence the class of sectors with positive energy is stable under composition, conjugation and direct integral decomposition. Received: 21 April 1997 / Accepted: 23 September 1997     

Identity principles for commuting holomorphic self-maps of the unit disc

Let f,g be two commuting holomorphic self-maps of the unit disc. If f and g agree at the common Wolff point up to a certain order of derivatives (no more than 3 if the Wolff point is on the unit circle), then f≡g.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Classes de symétrie des solides piézoélectriquesSymmetry classes of piezoelectric solids

We apply here the harmonic and Cartan decomposition techniques to piezoelectric material symmetries classification. We show in particular that we shall reduce from 19 to 17 the number of symmetry classes corresponding to the piezoelectric phenomenon. To cite this article: G. Geymonat, T. Weller, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 847–852.     

Multiple image encryption using an aperture-modulated optical system

A multiple image cryptosystem based on different apertures in an optical set-up under a holographic arrangement is proposed. The system is a security architecture that uses different pupil aperture mask in the encoding lens to encrypt different images. Based on this approach multiple encryption is achieved by changing the pupil aperture arrangement of the optical system among exposures. In addition to the classical speckle phase mask, the geometrical parameters characterizing the apertures are introduced to increase the system security. Even when an illegal user steals the speckle phase mask, the system cannot be broken into without the correct pupil geometrical parameters. The experimental set-up is based on a volume photorefractive BSO crystal as storing device. Information retrieval is done via a phase conjugation operation. We also have to stress that the multiple storage under this scheme, is only possible with the help of the aperture mask. Simulation and experimental results are further introduced to verify the proposed method.     

Sulla K-variazione Essenziale di Una Funzione reale

In this paper we consider a definition of essentialK-variation for real functions which gives information on the absolute integrability of its approximate derivate on a measurable set.     

A convenient strategy of dimerization by microwave heating and using 2,5-diketopiperazine as scaffold

A novel and convenient microwave-assisted dimerization of an active peptide compound using the DKPs as scaffold is described. The key reaction giving rise to the diketopiperazine scaffold is the intermolecular coupling. No epimerization was detected in the reactions used. Conventional and microwave heating of the reactions are compared. Synthesis by microwave irradiation gave the desired compounds in higher yields and in shorter reaction times than those obtained by conventional heating.     

Three terminals optoelectronics devices integrated into a silicon on silicon waveguide

In this paper we describe two different kind of optoelectronic devices both based on a three terminals active device and exploit the plasma dispersion effect to achieve the desired working. The first device exploits this effect in order to obtain an optical modulation. The second device is an optoelectronic router based on the mode-mixing principle together with the injection-induced optical phase shift. Both devices are integrated into a Silicon on Silicon optical channel waveguide which can be realized using a standard bipolar process. The possibility of using standard, well-known technology presents several advantages with respect to III–V Optoelectronics. The active three terminal device used is a Bipolar Mode Field Effect Transistor (BMFET). Numerical simulation results are presented on both devices.     

Su di una questioke algebrica,che si presenta in problem di stabilità

Rendiconti del Circolo Matematico di Palermo Series 1 -