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.     

Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

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.     

Sets of sampling and interpolation in Bergman spaces

Properties of the unions of sampling and interpolation sets for Bergman spaces are discussed in conjunction with the examples given by Seip (1993). Their relationship to the classical interpolation sequences is explored. In addition, the role played by canonical divisors in the study of these sets is examined and an example of a sampling set is constructed in the disk.

     

Common luminescence intensity fluctuations of single particle and single molecules in non-conducing matrices

Optical spectroscopy in combination with wide field or confocal optical microscopy enables the investigation of single quantum objects such as organic molecules, II/VI semiconductor quantum dots and silicon nanocrystals. They all have fluctuations of luminescence intensities on time scales longer than μs in common. A comparison reveals that despite the large differences of the nature of the respective quantum objects, the intensity fluctuations are related to a slow ionisation process followed by a trapping of the photoejected charge in the non-conducing environment. Detailed aspects of the dynamics are controlled by the dielectric properties of the matrix.     

Amorphous Fe–Mg alloy thin films: magnetic properties and atomic vibrational dynamics

Amorphous (a-) Fe _x Mg_1?x alloys are interesting materials for the investigation of non-Debye-like low-energy vibrational excitations. We have prepared a-Fe _x Mg_1?x alloy thin films (0.3 ≤ × ≤0.7) by vapour quenching. The amorphous state was confirmed by conversion electron Mössbauer spectroscopy between 4.2–300 K, and the x- and temperature-dependence of the isomer shift and hyperfine magnetic field was measured. For x= 0.6 and 0.7, magnetic ordering occurs below ~150 K. The atomic vibrational density of states, g(E), was determined by nuclear resonant inelastic scattering, providing clear evidence for the non-Debye-like low-energy vibrational excitations.     

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.