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1.
Roberto Morales-Cerrada Dr. Christophe Fliedel Dr. Jean-Claude Daran Dr. Florence Gayet Dr. Vincent Ladmiral Dr. Bruno Améduri Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):296-308
Thermal decarbonylation of the acyl compounds [Mn(CO)5(CORF)] (RF=CF3, CHF2, CH2CF3, CF2CH3) yielded the corresponding alkyl derivatives [Mn(CO)5(RF)], 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)(RF)] and [Mn(12CO)4(ax-13CO)(RF)] isotopomers and a ranking of the RF donor power in the order CF3<CHF2<CH2CF3≈CF2CH3. The homolytic Mn−RF bond cleavage in [Mn(CO)5(RF)] at various temperatures under saturation conditions with trapping of the generated RF 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−RF bond cleavage was further demonstrated by the observation that [Mn(CO)5(CF3)] (the compound with the strongest Mn−RF 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. 相似文献
2.
J. Maul I. Strachnov S. Karpuk P. Bernhard A. Oelsner G. Schönhense G. Huber 《Applied Physics A: Materials Science & Processing》2006,82(1):43-47
We report morphologic changes of metallic surfaces at the onset of ablation, starting from gentle ablation to the emergence of ablation craters. The evolution of both observed melting zones and of ablation craters therein are investigated in dependence of the ablation laser fluence for nanosecond ultraviolet laser pulses. Further, consequences of crater formation for cluster synthesis within the released atomic vapor are pointed out. PACS 52.38.Mf; 79.20.Ds; 65.40.De 相似文献
3.
The control of piecewise-deterministic processes is studied where only local boundedness of the data is assumed. Moreover the discount rate may be zero. The value function is shown to be solution to the Bellman equation in a weak sense; however the solution concept is strong enough to generate optimal policies. Continuity and compactness conditions are given for the existence of nonrelaxed optimal feedback controls. 相似文献
4.
Potential for micromachined actuation of ultra-wide continuously tunable optoelectronic devices 总被引:1,自引:0,他引:1
H. Hillmer J. Daleiden C. Prott F. Römer S. Irmer V. Rangelov A. Tarraf S. Schüler M. Strassner 《Applied physics. B, Lasers and optics》2002,75(1):3-13
Tailored scaling represents a principle of success that, both in nature and in technology, allows the effectiveness of physical
effects to be enhanced. Mutation and selection in nature are imitated in technology, e.g. by model calculation and design.
Proper scaling of dimensions in natural photonic crystals and our fabricated artificial 1D photonic crystals (DBRs, distributed
Bragg reflectors) enable efficient diffractive interaction in a specific spectral range. For our optical microsystems we illustrate
that tailored miniaturization may also increase the mechanical stability and the effectiveness of spectral tuning by thermal
and electrostatic actuation, since the relative significance of the fundamental physical forces involved considerably changes
with scaling. These basic physical principles are rigorously applied in micromachined 1.55-μm vertical-resonator-based devices.
We modeled, implemented and characterized 1.55-μm micromachined optical filters and vertical-cavity surface-emitting laser
devices capable of wide, monotonic and kink-free tuning by a single control parameter. Tuning is achieved by mechanical actuation
of one or several air-gaps that are part of the vertical resonator including two ultra-highly reflective DBR mirrors of strong
refractive index contrast: (i) Δn=2.17 for InP/air-gap DBRs (3.5 periods) using GaInAs sacrificial layers and (ii) Δn=0.5
for Si3N4/SiO2 DBRs (12 periods) with a polymer sacrificial layer to implement the air-cavity. In semiconductor multiple air-gap filters,
a continuous tuning of >8% of the absolute wavelength is obtained. Varying the reverse voltage (U=0–5 V) between the membranes
(electrostatic actuation), a tuning range of >110 nm was obtained for a large number of devices. The correlation of the wavelength
and the applied voltage is accurately reproducible without any hysteresis. In two filters, tuning of 127 and 130 nm was observed
for about ΔU=7 V. The extremely wide tuning range and the very small voltage required are record values to the best of our
knowledge. For thermally actuated dielectric filters based on polymer sacrificial layers, Δλ/ΔU=-7 nm/V is found.
Received: 10 May 2002 / Published online: 8 August 2002 相似文献
5.
E. Goering M. Justen J. Geissler U. Rüdiger M. Rabe G. Güntherodt G. Schütz 《Applied Physics A: Materials Science & Processing》2002,74(6):747-753
Highly a-axis-textured CrO2 films have been deposited on Al2O3 (0001) substrates by chemical vapor deposition. CrO2 has been found to have highly a-axis (010)-oriented columnar growth on a Cr2O3 (0001) initial layer. The six-fold surface symmetry of the Cr2O3 initial layer leads to three equivalent in-plane orientations of the a-axis-oriented CrO2 unit cell. We report Cr L2,3 X-ray magnetic circular dichroism data along the surface normal and at 60° off-normal sample orientation. For a 60° sample
alignment, a strong increase of the projected orbital moment could be observed for unoccupied majority t2g states using moment analysis. Therefore, the c axis is identified as the intrinsic magnetic easy axis of CrO2. In addition, a small spin moment and a very strong magnetic dipole term Tz have been found.
Received: 8 January 2002 / Accepted: 8 January 2002 相似文献
6.
Hyperfine Interactions - In this paper, the conditions for which three-dimensional crystalline ion beams were attained in the rf quadrupole storage ring PALLAS at a velocity of around 2800 m/s are... 相似文献
7.
Ledzewicz U. Nowakowski A. Schättler H. 《Journal of Optimization Theory and Applications》2004,122(2):345-370
It is shown that, if a parametrized fämily of extremals F can be stratified in a way compatible with the flow map generated by F, then those trajectories of the family which realize the minimal values of the cost in F are indeed optimal in comparison with all trajectories which lie in the region R covered by the trajectories of F. It is not assumed that F is a field covering the state space injectively. As illustration, an optimal synthesis is constructed for a system where the flow of extremals exhibits a simple cusp singularity. 相似文献
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