Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

Multiple expansions of real numbers with digits set $$\left\{ 0,1,q\right\} $$ 0 , 1 , q

Mathematische Zeitschrift - For $$q>1$$ we consider expansions in base q with digits set $$\left\{ 0,1,q\right\} $$ . Let $${{\mathcal {U}}}_q$$ be the set of points which have a unique...     

A natural extension for the greedy β-transformation with three arbitrary digits

We construct a planar version of the natural extension of the piecewise linear transformation T generating greedy β-expansions with digits in an arbitrary set of real numbers A = {a ₀, a ₁, a ₂}. As a result, we derive in an easy way a closed formula for the density of the unique T-invariant measure µ absolutely continuous with respect to Lebesgue measure. Furthermore, we show that T is exact and weak Bernoulli with respect to µ.     

Equipartition of interval partitions and an application to number theory

We give wider application and simpler proofs of results describing the rate at which the digits of one number-theoretic expansion determine those of another. The proofs are based on general measure-theoretic covering arguments and not on the dynamics of specific maps.

     

Ultrafast laser assisted fabrication of ZnO nanorod arrays for photon detection applications

Orderly aligned ZnO nanorod arrays were grown by the ultrafast laser assisted ablation deposition method. These nanorod arrays were further used to make efficient p-n heterojunction photodetector arrays, which have the potential to have nanoscale spatial resolution for imaging, unique incident polarization discrimination capability, and much improved quantum efficiency as well as detection sensitivity. Both front- and back-illumination photodetection schemes were demonstrated by growing those ZnO nanorod arrays on p-type silicon and p-type Zn_0.9Mg_0.1O-coated Al₂O₃ (0 0 0 1) substrates, respectively. Typical diode rectification behavior and photosensitivity were observed in both designs through I-V and photocurrent measurements.     

Unexpected one-pot synthesis of A3-type unsymmetrical porphyrin

The first direct synthesis of A₃-type unsymmetrical porphyrin is achieved via conventional pyrrole–aldehyde condensation in a one-pot procedure in an appreciable yield. Generalization of this approach to a variety of other aldehydes revealed that it is advantageous for highly electron-rich aldehydes giving unsymmetrical porphyrin, while electron-poor aldehydes even failed to cyclize under the same experimental conditions.     

Appended corrole manganese complexes:Catalysis and axial-ligand effect

A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.