40 years with porphyrazines

Abstract

Our laboratory started research on tetraazaporphyrins in the middle of the 1970s. Before our works there was no information in the literature about coordination and ionization properties of these compounds, formation of their metal complexes or their state and behavior in proton-donating and proton-acceptor media. We carried out the first studies of the coordination and acid-base properties of unsubstituted tetraazaporphine [1], its octaphenyl [2] and tetra(tetramethylene)-[3] substituted derivatives. In this micro-review we summarize our works on the peripheral functionalization of unsubstituted porphyrazines and on their acid-base and coordination properties.

Nipagin-Functionalized Porphyrazine and Phthalocyanine—Synthesis, Physicochemical Characterization and Toxicity Study after Deposition on Titanium Dioxide Nanoparticles P25

“…Interestingly, in all studied solvents containing 7, the Q band remained unsplit (Figure 1b). This observation is in agreement with the data collected by Khelevina and Malyasova, who reported that Pzs reveal low basicity and, therefore, a high concentration of acid has to be used to induce their protonation [41].…”

DFT Quantum-Chemical Modeling Molecular Structures of Cobalt Macrocyclic Complexes with Porphyrazine or Its Benzo-Derivatives and Two Oxygen Acido Ligands

“…These complexes are interesting in that, as it is easy to see from these formulas, in any of these complexes the cobalt atom is bonded to other atoms by eight chemical bonds, six of which are formed by the exchange mechanism (namely, two with each of two oxygen atoms and one with the each of two nitrogen atoms), and according to the generally accepted definition, the concept of "oxidation state", the value of this parameter for a given atom of a 3d-element should be accepted equal to (+6). It should be specially noted that no mention of complexes of type I-III in the special literature devoted to (NNNN)-donor atomic macrocyclic ligands-porphyrins, porphyrazines and their derivatives [14][15][16][17][18][19][20][21][22], or anywhere else, could not be found. In this connection, the given article will be devoted to a theoretical analysis regarding the possibility of the existence in principle of such complexes with the use of modern methods of quantum chemistry, namely, the density functional theory (DFT) method.…”

Olga Grigoryevna Khelevina – Teacher, Mentor and Scientist

“…В течение многих лет научная группа изучала влияние азазамещения в ароматических макроциклах типа порфиринов на строение, физико-химические свойства и реакционную способность порфириновых молекул и их комплексов. [1,2] Исследованиями этого коллектива заложены научные основы нового направления «Координационная химия азапорфиринов», где установлена взаимосвязь между строением реакционного центра и координирующей способностью азапорфиринов, что позволило целенаправленно, варьируя строение реакционного центра путем модификации макроцикла, изменять их координационные свойства для решения прикладных задач с применением комплексов азапорфиринов. [3][4][5][6] Разработанные методы синтеза металлокомплексов азапорфиринов и новые материалы на их основе защищены рядом авторских свидетельств.…”

“…For many years, her scientific group studied the effect of azasubstitution in aromatic porphyrin-type macrocyclic complexes on their structure, physicochemical properties and reactivity. [1,2] The relationship between the structure of the reaction center and the coordinating ability of azaporphyrin macroheterocycles was established, and that was quite important for development of practical applications of azaporphyrin complexes. [3][4][5][6] The new developed methods for the synthesis of azaporphyrins, their metal complexes and new materials based on them are protected by a number of patents (author's certificates).…”