Perfluorinated porphyrazines 1: Synthesis and UV-vis spectral study of perfluorinated octaphenylporphyrazine and its indium(III) complex, [MPA(F₅Ph)₈](M= 2H,In^III(OH))

Abstract

Novel perfluorinated porphyrazine has been prepared as indium(III) complex of octa(pentafluorophenyl)porphyrazine by cyclotetramerization of 1,2-dicyano-1,2-bis(pentafluorophenyl)-ethylene (mixture of cis- and trans-isomers) with basic indium(III) acetate in a melt. The In III complex is stable in trifluoroacetic and sulfuric acids, but is easily demetalated with formation of the free-base in a chloroform solution containing HCl or slighly acidified with CF 3 COOH in the presence of tetraalkylammonium chloride as a catalyst. Perfluorination of octaphenylporphyrazine macrocycle leads to a hypsochromic shift of the Q-band maxima in the electronic absorption spectra, to drastic decrease of the basicity of meso-nitrogen atoms of porphyrazine macrocycle and to increase of the acidity of the internal NH -groups.

Phosphorus(V) tetrapyrazinocorrolazines — first corrolazine derivatives with fused heterocyclic rings

“…7) has a linear character with a slope ~1 evidencing monoprotonation. The value of pK s = -0.04±0.03 indicates that basicity of meso-nitrogen atom in corrolazine macrocycle is much lower than in octaphenylporphyrazine [Ph 8 PAH 2 ] and its metal complexes (pK s = +1.1 ÷ +1.5 [27,38,39]). Taking into account that the formal charge on the macrocycle in corrolazine complexes (-3) is more negative than in porphyrazine complexes (-2), one can conclude that the negative charge is effectively compensated in P V corrolazine, existing in acid medium, very likely, as cationic hydroxyphosphorus(V) complex [(Ph 8 CA) P + (OH)] with positively charged P atom.…”

Synthesis, Structure, and Spectral-Luminescent Properties of Peripherally Fluorinated Mg(II) and Zn(II) Octaphenyltetraazaporphyrins

“…The specific chemical behavior of substituted metalloporphyrins is mainly caused by the presence of a complex branched macrocycle and strong conjugation of the π–electron system [ 12 ]. The method of template cyclotetramerization of porphyrin molecule fragments with a metal or its salt has been used to synthesize ionic and covalent complexes based on porphyrins [ 13 , 14 , 15 ] and tetraazaporphyrins [ 16 , 17 , 18 , 19 , 20 ]. In this work, cyclization of di-(2,6-difluorophenyl)maleindinitrile with acetates of the respective metals in boiling ethylene glycol was applied to synthesize and identify Mg(II)- and Zn(II)-octa-(2,6-difluorophenyl)tetraazaporphyrin complexes.…”

The p-Metal Porphyrins: from Specificity of Properties to Application in Medicine, Catalysis, and Optoelectronics

“…[17] The highest stability of the main-group porphyrin complexes can be illustrated by the fact that the coordination state retains in cool sulphuric acid (SM, Table S2). [8,21] One of the strongest acids -perchloric acid leads to stoichiometric proton-dependent condensation of the five-coordinate Group 13 metalloporphyrin species, M(P)(OH), where M is Al, Ga, and In in the corresponding m-hydroxo dimmers, [M(P) 2 (OH)] + , without the coordination center dissociation. [22] Using basic or reductive conditions is necessary to remove a metal cation from the MP coordination center.…”