From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 82271 10.52957/27821900_2022_03_93 Научные статьи Scientific articles Научные статьи Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media Specific features of the kinetics of destructive degradation of porphine and phthalocyanine derivatives in oxidizing media Березин Дмитрий Борисович Berezin Dmitry Borisovich

доктор химических наук;

doctor of chemical sciences;

 Березин Борис Дмитриевич Berezin Boris Dmitrievich Разговоров Павел Борисович Razgovorov Pavel Borisovich razgovorovpb@ystu.ru

доктор технических наук;

doctor of technical sciences;

 Ивановский государственный химико-технологический университет Ivanovo State University of Chemistry and Technology Ярославский государственный технический университет Yaroslavl State Technical University 23 09 2022 23 09 2022 3 3 93 105 29 08 2022 12 09 2022 https://chemintech.ru/en/nauka/article/82271/view

The paper presents the analysis on chemical, thermal and electrochemical stability of some aromatic macroheterocycles (MHC) of porphyrin (H2P) class as well as their benzo- and aza-analogues, establishes electronic and structural factors determining the rate of pigment destruction in the presence of oxidant. The values of redox potentials of porphyrin-, tetraaz-, tetrabenzo-porphyrin- and phthalocyanine-type MHCs correlate with the temperatures at which their thermo-oxidative degradation starts and the decomposition rates in oxidizing media. The combined benzo- and azamer substitution in H2P molecules leads to their destabilisation with respect to oxidants, the situation depending strongly on the nature of the oxidant (H2O2, S2O82- and NO3-), the solvent (H2SO4, HOAc) as well as the nature of the metal in the molecule. The polymer state or spatial distortion of the MHC has a significant influence on the resistance to oxidising agents. The reaction mechanisms of oxidation of label-free porphyrins and phthalocyanines by hydrogen peroxide are shown to be identical. In both cases, the reaction centres of MHCs are N H bonds, either in the meso-position (H2Ps) or in the coordination cavity of the H2N4 molecule (H2P), and the pigments are cleaved to colourless products.

The paper presents the analysis on chemical, thermal and electrochemical stability of some aromatic macroheterocycles (MHC) of porphyrin (H2P) class as well as their benzo- and aza-analogues, establishes electronic and structural factors determining the rate of pigment destruction in the presence of oxidant. The values of redox potentials of porphyrin-, tetraaz-, tetrabenzo-porphyrin- and phthalocyanine-type MHCs correlate with the temperatures at which their thermo-oxidative degradation starts and the decomposition rates in oxidizing media. The combined benzo- and azamer substitution in H2P molecules leads to their destabilisation with respect to oxidants, the situation depending strongly on the nature of the oxidant (H2O2, S2O82- and NO3-), the solvent (H2SO4, HOAc) as well as the nature of the metal in the molecule. The polymer state or spatial distortion of the MHC has a significant influence on the resistance to oxidising agents. The reaction mechanisms of oxidation of label-free porphyrins and phthalocyanines by hydrogen peroxide are shown to be identical. In both cases, the reaction centres of MHCs are N H bonds, either in the meso-position (H2Ps) or in the coordination cavity of the H2N4 molecule (H2P), and the pigments are cleaved to colourless products.

 tetrapyrrolemacroheterocyclic compounds; porphyrins; phthalocyanines; oxidative degradation redox potentials This work was supported by Ivanovo State University of Chemistry and Technology, Ivanovo, Russia Centre for the Collective Use of Scientific Equipment (the Russian Ministry of Education and Science, Agreement No. 075-15-2021-671)

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