Emission spectra of the cations of 2,5- and 3,5-difluorophenol, of 2,3,4- and 2,4,5-trifluorophenol, of 2,3,5,6-tetrafluorophenol and of 2,3,4,5,6-pentafluorophenol have been obtained in the gas phase using low-energy electron beam excitation. The band systems are assigned to the B?(π?1) → X?(π?1) electronic transitions of these cations by reference to photoelectron spectroscopic data. The He(Iα) photoelectron spectra and the ionisation energies of ten fluoro-substituted phenols are reported. The symmetries of the four lowest electronic states of these cations are inferred from the radiative decay studies. The lifetimes of the lowest vibrational levels of the B?(π?1) state of the six fluoro-substituted phenol cations above have also been measured. 相似文献
The electrodynamics of single-layer graphene is studied in the scaling regime. At any finite temperature, there is a weakly damped collective thermoplasma polariton mode whose dispersion and wavelength-dependent damping is determined analytically. The electric and magnetic fields associated with this mode decay exponentially in the direction perpendicular to the graphene layer, but, unlike the surface plasma polariton modes of metals, the decay length and the mode frequency are strongly temperature-dependent. This may lead to new ways of generation and manipulation of these modes. 相似文献
A number of characterizations involving column and null spaces of various functions of a pair of oblique projectors are established. Particular attention is paid to properties of a product of the two projectors, but other functions of the pair (such as sum, difference or sum and difference of products) are considered as well. In many cases, the results obtained generalize those already known to be valid for orthogonal projectors. 相似文献
Polynomials in two variables, evaluated at A and with A being a square complex matrix and being its transform belonging to the set {A=, A†, A∗}, in which A=, A†, and A∗ denote, respectively, any reflexive generalized inverse, the Moore-Penrose inverse, and the conjugate transpose of A, are considered. An essential role, in characterizing when such polynomials are satisfied by two matrices linked as above, is played by the condition that the column space of A is the column space of . The results given unify a number of prior, isolated results. 相似文献
Summary: We report on the synthesis of a new amphiphilic, polymer‐bound variant of the Hoveyda‐Grubbs catalyst via the coupling reaction of a carboxylic acid‐functionalized poly(2‐oxazoline) block copolymer with 2‐isopropoxy‐5‐hydroxystyrene and subsequent reaction of the resulting macroligand with a second generation Grubbs catalyst. For the benchmark, the substrate diethyl diallylmalonate was studied in the ring‐closing metathesis (RCM) reaction and a turn‐over number (TON) of up to 390 in water was achieved. To the best of our knowledge, this is the highest value for any aqueous RCM reaction to date. For the first time, recycling of a ruthenium initiator in an aqueous RCM reaction has been successful to some extent. In addition, the micellar conditions accelerate the conversion of the hydrophobic diene and at the same time stabilize the active alkylidene species, although competing decomposition of the catalyst in water still impairs the catalyst performance. Residual ruthenium content was determined to be below 1 ppm in the product suggesting a very low leaching of the polymeric catalyst system.
Simplified chemical structure of the amphiphilic, polymer‐bound Grubbs‐Hoveyda catalyst. 相似文献
On the basis of simulated data two ways of evaluating individual rate constants by combining kp2/kt and kp /kt (kp , kt = rate constants of chain propagation and termination, respectively) were checked considering the chain‐length dependence of kt. The first way tried to make use of the fact that pseudostationary polymerization yields data for kp2/kt as well as for kp /kt referring to the very same experiment, in the second way kp2/kt (from steady state experiments) and kp/kt data referring to the same mean length of the terminating radical chains were compared. In the first case no meaningful data at all could be obtained because different averages of kt are operative in the expressions for kp /kt and kp2/kt. In spite of the comparatively small difference between these two averages (≈15% only) this makes the method collapse. The second way, which can be regarded as an intelligent modification of the “classical” method of determining individual rate constants, at least succeeded in reproducing the correct order of magnitude of the individual rate constants. However, although stationary and pseudostationary experiments independently could be shown to return the same kt for the same average chain‐length of terminating radicals within extremely narrow limits no reasonable chain‐length dependence of kt could be derived in this way. The reason is an extreme sensitivity of the pair of equations for kp/kt and kp2/kt towards small errors and inconsistencies which renders the method unsuccessful even for the high quality simulation data and most probably makes it even collapse for real data. This casts a characteristic light on the unsatisfactory situation with respect to individual rate constants determined in the classical way, regardless of a chain‐length dependence of termination. As a consequence, all efforts of establishing the chain‐length dependence of kt are recommended to avoid this way and should rather resort to methods based on inserting a directly determined kp into the equations characteristic of kp2/kt or kp/kt, properly considering the chain‐length dependent character of kt. 相似文献