N. A. Pavlycheva

Kinetics of thermal oxidative decomposition of zinc porphyrin and phthalocyanine complexes

Thermal oxidative decomposition of certain zinc porphyrin and phthalocyanine complexes was studied using an installation for thermal analysis, and kinetic parameters of the thermal oxidation of these compounds were determined. The introduction of peripheral alkyl substituents into porphyrin molecules enhances the macroring stability with respect to the thermal oxidation. In cases of benzoporphyrins and phthalocyanines, this effect is leveled off because of spatial remoteness of the substituent from the reactive center of the macroring. The substances studied decompose in several steps; the initial step corresponds to the oxidation of peripheral substituents of the macroring. For the majority of the substances studied, the order of the thermal oxidation reaction is 1, and the main step controlling the thermal oxidation process is diffusion.

On the Nature of Interaction Between Fullerene and Aniline

Abstract Interaction between fullerene C60 and N,N‐dialkyl‐substituted anilines was studied by gas–liquid chromatography (GLC) and titration calorimetry. The GLC study was performed at 140–200°C in the poly(tetramethylbenzene) solvent with ultra‐high solubility of C60. No interaction of the C60–aniline type was registered under such conditions. Calorimetric titration performed at 25°C in a non‐aromatic solvent confirmed the lack of complex formation. Minute exoeffect registered is explained by suppressing of the rotation motion of the C60 molecules accompanied by energy dissipation for the aniline environment.

Molecular complexes of phthalocyanine with organic solvents

It was established that in crystal solvates and solutions zinc(II)tetra-tert-butylphthalocyanine formed stable molecular complexes with benzene and pyridine. The characteristics of the corresponding molecular complexes were estimated. Molecules of electron-donor and aromatic solvents do not break down the zinc(II)tetra-tert-butylphthalocyanine associates and do not facilitate intraphase polymorphic transition. A comparative analysis was carried out for the coordinative properties of zinc(II)tetra-tert-butylphthalocyanine and its structural analog, zinc(II)tetrabenzoporphyrin, with respect to pyridine in benzene solutions.

Thermogravimetric and Spectral Studies of the Reaction between Benzotriazolyl Derivatives of Phthalodinitriles and Copper(II) Acetate

The interaction of benzotriazolyl derivatives of phthalodinitriles with copper(II) acetate was studied thermogravimetrically and spectroscopically. Electron acceptor properties of peripheral substituents had a predominant influence on the enthalpy parameter of formation of copper(II)phthalocyanines.

Coordination ability of zinc(ii) porphyrins with respect to electron-donating ligands. Influence of the structure and solvation effects

Thermodynamics of the formation of molecular complexes of synthetic and natural zinc(ii) porphyrins with n-propylamine and glycine methyl ester in benzene was investigated. Study of the π—π complexes of zinc(ii) porphyrins with benzene demonstrated that thermodynamic stability of the axial complexes depends on both the structure of the porphyrin macrocycle and the ability of the corresponding metalloporphyrins to form energetically stable π—π complexes with aromatic molecules.