EC-backward-E electrochemistry through electrocatalytic formal [2+2] cycloaddition reaction between anodically activated aliphatic enol ethers and unactivated olefins possessing an alkoxyphenyl group was clearly described by using cyclic voltammetric studies and spin density observation with B3LYP/6-31G(d) calculations. The alkoxyphenyl group was found to regulate the electron transfer, which operates as an electron donor during the formation of the cyclobutane ring and as an electron acceptor from the anode to give the final product (EC-backward-E). 相似文献
In order to achieve high-density recording, the detailed behavior of thermal degradation should be investigated. In this paper, the degradation of magnetization of high-density recording medium is examined using the 3-D finite element method (FEM) combined with the modeling of Stoner–Wohlfarth (SW) particles and Neel–Arrhenius switching probability. It is shown that the anisotropy field Hk suppressed the thermal degradation and the saturation magnetization Ms enhances it. The thermal degradation is also changed by the amplitude of magnetization. 相似文献
Described herein is that the catalytic construction of N‐substituted five‐ and six‐membered lactams from keto acids with primary amines by reductive amination, using an indium/silane combination. This relatively benign and safe catalyst/reductant system tolerates the use of a variety of functional groups, especially ones that are reduction‐sensitive. A direct switch from synthesizing lactams to synthesizing cyclic amines is achieved by changing the catalyst from In(OAc)3 to InI3. This conversion occurs by further reduction of the lactam using the indium/silane pair. 相似文献
Subdifferentials of a singular convex functional representing the surface free energy of a crystal under the roughening temperature are characterized. The energy functional is defined on Sobolev spaces of order ?1, so the subdifferential mathematically formulates the energy?s gradient which formally involves 4th order spacial derivatives of the surface?s height. The subdifferentials are analyzed in the negative Sobolev spaces of arbitrary spacial dimension on which both a periodic boundary condition and a Dirichlet boundary condition are separately imposed. Based on the characterization theorem of subdifferentials, the smallest element contained in the subdifferential of the energy for a spherically symmetric surface is calculated under the Dirichlet boundary condition. 相似文献
Compensation of the intracavity dispersion in the mode-locked oscillator is known to be one of the most important factors for ultrashort pulse generation. However, recent investigations of a Yb-doped fiber mode-locked oscillator revealed that precise third-order dispersion (TOD) compensation is not always necessary for ultrashort pulse generation, owing to the strong nonlinearity that compensates residual TOD without reducing its spectral bandwidth. The origin of the nonlinear TOD compensation has remained unclear. To investigate the process in detail, we studied the pulse evolution inside a 30 fs Yb-doped fiber mode-locked oscillator both experimentally and numerically, and we found that the nonlinear phase shift with a temporally asymmetric pulse shape introduces an appropriate amount of TOD that exactly cancels the residual cavity dispersion. 相似文献
A porous copper coordination framework grew epitaxially as a single crystal on the surface of a single crystal of a porous zinc coordination framework, as described by S. Kitagawa and co‐workers in their Communication on page 1766 ff. The picture shows the structural relationship between the copper and zinc frameworks, which has been unveiled by synchrotron surface X‐ray diffraction measurements; in‐plane rotational epitaxial growth compensates for the different lattice constants of the two crystals.
We report the geometrical features and electronic structures of di-mu-oxo-bridged Mn-Mn binuclear complexes with H2O ligands [Mn2O2(H2O)8]q+ in the iso- and mixed-valence oxidation states. All of the combinations among Mn(II), Mn(III), and Mn(IV) ions are considered the oxidation states of the Mn-Mn center, and the changes in molecular structure induced by the different electron configurations of Mn-based orbitals are investigated in relation to the oxygen-evolving complex (OEC) of photosystem II. The stable geometries of complexes are determined by using the hybrid-type density functional theory for both of the highest- and lowest-spin couplings between Mn sites, and the lowest-spin-coupled states are energetically more favorable than the highest-spin-coupled states except in the case of the complexes with the Mn(II) ion. The coordination positions of H2O ligands at the Mn(II) site tend to shift from the octahedral positions in contrast to those at the Mn(III) and Mn(IV) sites. The shape of the Mn2O2 core and the distances between the Mn ions and the H2O ligands vary depending on the electron occupations of the octahedral eg orbitals on the Mn site with an antibonding nature for the Mn-ligand interactions, indicating the trend as Mn(II)-O > Mn(III)-O and Mn(IV)-O, O-Mn(II)-O > O-Mn(III)-O > O-Mn(IV)-O among the iso-valence Mn2O2 cores, and O-Mn(lower)-O < O-Mn(higher)-O within the mixed-valence Mn2O2 core, and as Mn(II)-OH2 and Mn(III)-OH2 > Mn(IV)-OH2 for the axial H2O ligand. The optimized geometries of model complexes are compared with the X-ray structure of the OEC, and it is suggested that the cubane-like Mn cluster of the active site may not contain a Mn(II) ion. The effective exchange integrals are estimated by applying the approximate spin projection to clarify the magnetic coupling between Mn sites, and the superexchange pathways through the di-mu-oxo bridge are examined on the basis of the singly occupied magnetic orbitals derived from the singlet-coupled natural orbitals in the broken-symmetry state. The comparisons of the calculated results between [Mn2O2(H2O)8]q+ in this study and [Mn2O2(NH3)8]q+ reported by McGrady et al. suggest that the symmetric pathways are dominant to the exchange coupling constant, and the crossed pathway would be less important for the former than it would for the latter in the Mn(III)-Mn(III), Mn(IV)-Mn(IV), and Mn(III)-Mn(IV) oxidation states. 相似文献
Multifrequency (X-, Q-, and W-band) electron spin resonance (ESR) spectroscopy has been used to characterize the phenoxyl radical produced from alpha-(3,5-di-tert-butyl-4-hydroxyphenyl)-N-tert-butylnitrone, which is a new spin-trapping reagent. The X-band measurement did not resolve the powder-pattern ESR spectrum. Because of its higher resolution with g value, the Q-band ESR study revealed that the g factor has an axial-like symmetry and that the observed hyperfine structure in the Z-direction is caused by the nitrogen nucleus at the para-position. Furthermore, the results of the W-band ESR experiment more clearly distinguished the perpendicular components from the parallel component, resolving the perpendicular components into x and y components. The X-band powder spectrum was similar to the X-band ESR spectrum of the radical in a frozen solution of toluene. The computer simulation spectra performed using the obtained parameters fitted the experimental spectra well. A comparison of the amplitude of g( perpendicular)(gx, gy) with that of gz showed that the unpaired electron is delocalized over the pi-conjugated framework. Considering the hyperfine coupling constant, it was concluded that about 16% of the unpaired electron distributed over the nitrogen nucleus at the para-position. This study thus showed the significant potential of a multifrequency ESR approach to a powder sample radical in terms of its high resolution with g value. 相似文献