The photoelectron spectra of the diazanaphthalenes

The high-resolution He 584 Å photoelectron spectra of ten diazanaphthalenes are presented. The ordering of the π orbitals and the nitrogen “lone-pair” orbitals is discussed. Several semi-empirical quantum-chemical calculation methods have been screened against the experimental evidence

Perfluoro effect in the photoelectron spectra of quinoline and isoquinoline

The high-resolution He 584Aophotoelectron spectra of heptafluoroquinoline and heptafluoroisoquinoline are compared with those of the parent compounds. Shifts in π ionisation potentials, due to the fluorine substitution, can be described with an inductive and a combined inductive-conjugative Hu¨ckel model

Photoelectron spectra of fluorine substituted diazanaphthalenes: “Even cases”

The high resolution He 584 Å photoelectron spectra of three diazanaphthalenes and some of their fluorine derivatives are presented. The qualitative model that is used frequently in the discussion of lone-pair level splittings is examined

Raman spectra of zinc phthalocyanine monolayers adsorbed on glassy carbon and gold electrodes by application of a confocal Raman microspectrometer

Raman spectra of zinc phthalocyanine monolayers, adsorbed on gold and on glassy carbon surfaces (electrodes), are presented. These spectra have been recorded with the electrodes inside and outside an electrochemical cell filled with an aqueous electrolyte. A confocal Raman microspectrometer was used. It was demonstrated that, because this spectrometer uses low laser intensifies, no damage of the monolayer occurred. The results show that the interaction of the phthalocyanine molecule with gold differs from that with glassy carbon. Because the laser excitation wavelength (660 nm) coincides with a UV-visible absorption band (Q band), a strong resonance- enhanced Raman spectrum was obtained. No signs of surface enhancement (surface-enhanced Raman scattering) effects were detected

Oxygen reduction in an acid medium : electrocatalysis by CoNPc(1,2) impregnated on a carbon black support; effect of loading and heat treatment

O2 reduction in an acid medium has been investigated on a transition metal macrocycle, CoNPc(1,2), impregnated on a carbon black support with a high dibutylphthalate adsorption value, using a rotating disk electrode and voltammetry techniques described previously, combined with X-ray photoelectron spectroscopy measurements. Optimal activity was found for a bilayer coverage (n = 2) at 17%-18% w/w loading. Heat treatment seems to be beneficial for n 3: it increases the overall number N of exchanged electrons and improves the electrode wetting. For the most active samples, mixed Co(II)/Co(III) valencies were displayed

Photoelectron spectra of some fluorine substituted diazanaphthalenes

The high resolution He 584 Å photoelectron spectra of fluorine substituted 1,2-diaza-, 1,3-diaza-, 1,4-diaza- and 2,3-diaza-naphthalene are presented. By means of fluorine substitution the analysis of the photoelectron spectra of the parent compounds can be made more definite. Unexpected shifts of the nitrogen “lone-pair” bands can be explained within the through-space and through-bond interaction model. From this explanation one can deduce that fluorine substitution can give experimental evidence about the symmetry character of the “lone-pair” molecular orbitals

Photoelectron spectra of fluorine-substituted diazabenzenes

The high resolution He 584 Å photoelectron spectra of ten fluorine-substituted diazabenzenes are presented. By means of fluorine substitution the analysis of the photoelectron spectra of the parent compounds can be made more definite. “Lone-pair” ionization potentials are shown to correlate well with data calculated by a modified and iterative version of the extended Hückel method

Oxygen reduction in acid media: effect of iron substitution by cobalt on heat-treated naphthalocyanine impregnations supported on preselected carbon blacks

FeNPc(1.2) impregnations were investigated at various loadings using a rotating-disk electrode, voltammetry and X-ray photoelectron spectroscopy (XPS) techniques. Optimal activity takes place at monolayer coverage, and major demetallation occurs after prolonged exposure to acid solution. The substitution of Fe by Co enables the electrochemical performances to reach those presented by 10% Pt on Vulcan and stops the demetallation process. The application of fast atomic bombardment secondary ion mass spectrometry (FABS) together with XPS sheds light on the detrimental role of some electrophilic groups attached to the carbon black-catalyst interface

Oxygen reduction in acid media on supported iron naphthalocyanine: Effect of isomer configuration and pyrolysis

O2 reduction in H2SO4 medium has been investigated on FeNPc impregnations on Norit BrX by the rotating disk electrode technique. Important differences in activity and stability were found between the 1,2- and 2,3-FeNPc isomers (pyrolysed or not). XPS analyses show, for the most inactive sample, strong demetallation and nitrogen losses. This phenomenon can be attributed to the differences in flexibility between the FeNPc isomers, which influences their stabilization on the substrate

Oxygen reduction in acid media: influence of the heat treatment on the FeNPc(1–20 isomer mixture impregnated on carbon blacks and active charcoals

Oxygen reduction with the aid of a number of FeNPc(1–2) impregnated carbon supports in sulphuric acid solutions has been investigated.\ud \ud Loading of the carbon samples amounted to about 10 wt.%. After a 10 day stay in the aerated solutions the samples were investigated with rotating disk electrode and X-ray photoelectron spectroscopy techniques. The most active and stable samples correspond to mono- or submonolayers of FeNPc deposited on high dibutylphthalate adsorption carbon blacks. Comparison with data obtained previously on Norit BrX impregnations emphasizes the rôle of the electron density on the inner nitrogen atoms rather than that on the iron centres