Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

Zero-temperature properties of randomly self-interacting polymers

We study the zero-temperature behavior of several simple models for randomly self-interacting polymers in one and 1+1 dimensions. Results are based on exact enumeration and closed-form expressions.     

The calculation of frequency-dependent hyperpolarizabilities including electron correlation effects

The theory for the calculation of the frequency-dependent hyperpolarizabilities β(?2ω; 0, ω), β(?ω; 0, ω), and β(0; ω, ?ω) is discussed. New relations between these tensors are derived for those wave functions that obey the time-dependent Hellmann–Feynman theorem (e.g., the self-consistent field [SCF] or the exact wave function). Using second-order Møller–Plesset perturbation theory (MP2), expressions are obtained for the hyperpolarizabilities in terms of derivatives of appropriately defined linear polarizability tensors with respect to a static electric field. Results are presented for ammonia and formaldehyde for the optical Kerr effect and for secondharmonic generation. These results indicate that it is desirable to determine the frequency-dependent contribution to the hyperopolarizability at the MP2 rather than the SCF level of theory, in cases where the static hyperpolarizability has a large contribution from electron correlation and/or where the frequency-dependent contribution may be more significant, such as for secondharmonic generation.     

Luminescent copolymers for applications in multicolor‐light‐emitting devices

Light‐emitting diodes based on organic materials [organic light‐emitting diodes (OLEDs)] have attracted much interest over the past decade. Several different attempts have been made to realize multicolor OLEDs. This article describes a new approach based on energy transfer in a donor/acceptor system. A copolymer containing both donor and acceptor compounds as comonomer units is prepared. The polymer consists of a derivative of a luminescent dye [4‐dicyanmethylene‐2‐methyl‐6‐4H‐pyran (DCM); acceptor compound], which is copolymerized with fluorene (donor compound) to combine the properties of an electroactive polymer with a highly luminescent dye. Photochemical processing is achieved by UV irradiation of this copolymer in the presence of gaseous trialkylsilanes. This reagent selectively saturates the C?C bonds in the DCM comonomer units while leaving the fluorene units essentially unaffected. As a result of the photochemical process, the red electroluminescence of the acceptor compound vanishes, and the blue‐green electroluminescence from the polyfluorene units is recovered. Compared with previous approaches based on polymer blends, this copolymer approach avoids problems associated with phase‐separation phenomena in the active layer of OLEDs. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4317–4327, 2006     

Spin wave spectrum and exchange interactions in the antiferromagnetic garnet Ca3Cr2Ge3O12 by inelastic neutron scattering

We have measured the spin wave spectrum for the garnet Ca₃Cr₂Ge₃O₁₂ by means of inelastic neutron scattering. The data can be well described in the framework of linear spin wave theory if we assume a Heisenberg model with two exchange parameters up to the next nearest neighbours (J ₁ andJ ₂) and a staggered anisotropy field (A). A least squares fit to the observed dispersion relations yield the following values for these parameters: J ₁=–0.582(8)K,J ₂=0.416(4)K,A=0.25(8)K. Although symmetry requires that two nearest neighbour exchange constantsJ ₁ andJ ₁ ^' must be distinguished, only the average J ₁=(J ₁+3J ₁ ^' )/4 and the condition –0.35 K <J ₁=J ₁-J ₁ ^' <0.50 K could be deduced from the experiment. The most striking result is the positive value ofJ ₂. We discuss the implications for an understanding of superexchange mediated by more than one oxygen atom. In an extension of the conventional analysis we have calculated the integrated intensities in order to check the eigenvectors directly. Good agreement between observed and calculated intensities was obtained.     

Magnetic excitations and phase transition of CsFeBr3 in an external magnetic field

In CSFeBr₃ the Fe²⁺ ion with effective spin one has locally a singlet ground state (m=0). The antiferromagnetic interactions between neighbouring Fe-ions are too weak as compared with the anisotropy constant to introduce long range order in the absence of an external field. By inelastic neutron scattering we studied the magnetic excitations in an external magnetic field up to 5 Tesla applied along thec-axis. A linear Zeeman splitting was observed with a Landé factorg=2.4. The field renormalizes the dispersion curves in such a way that the exchange interaction has decreasing influence with increasing field. Theoretical calculations according to the excitonic model of Lindgård describe the experimental results very well. At 4.1 Tesla a phase transition appears to a commensurate long range order with a 120° arrangement of the spins in the hexagonal plane. Within the limits of experimental observation this phase transition has no influence on the dynamical behaviour. No critical phenomena could be observed. The dynamical structure factor |G _j()|² of the lower Zeeman split modes decreases with increasing field.     

Magnetic excitations in the quasi one-dimensional antiferromagnetic singlet groundstate system CsFeBr3

We have measured the magnetic excitations in CsFeBr₃ along the chain direction (z-axis) and perpendicular to it by inelastic neutron scattering. The measured dispersion curves can be reproduced by the formula $$\omega ^2 (q) = A^2 - 8A[J\cos (\pi q_c ) + J'\gamma (2\pi q_ \bot )]R(T)$$ which is very different from dispersion relations for usual 1 D antiferromagnets, because of the singlet groundstate of this system. The large value of the anisotropy energyA/k=29.8±0.5 K, which is independent of temperature, causes the singlet groundstate. The intra-and inter-chain exchange parameters areJ/k=?3.2±0.15K andJ'/k=?0.32±0.02 K determined atT=1.4 K. At 1.4 K the renormalisation factor is taken to beR(T)=1. AtT=30 K the value forR(T) was found to be 0.5±0.1 keepingJ andJ' unchanged. The excitations at (1/3 1/31) show soft mode behaviour but no phase transition. The observed intensities are interpreted by a heuristic model for the eigenvectors in the excited state including antiferro-as well as ferromagnetic configurations of the fluctuations.