Porphyrazines with bulky peripheral pyrrolyl substituents – Synthesis via microwave-assisted Suzuki-Miyaura cross-coupling reaction, optical and electrochemical properties

• Published in: Dyes and pigments Vol. 206; p. 110607
• Main Authors: Szczolko, Wojciech, Koczorowski, Tomasz, Wicher, Barbara, Kryjewski, Michal, Krakowska, Zuzanna, Tykarska, Ewa, Goslinski, Tomasz
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01.10.2022
• Subjects: Cross-coupling reactions; Macrocyclization reactions; Microwave-assisted organic synthesis; Porphyrazines; X-ray; Microwave-assisted organic synthesis; Porphyrazines; X-ray; Cross-coupling reactions; Macrocyclization reactions
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2022.110607

Synthesis of novel aminoporphyrazines with peripheral 3,4-dihalide-2,5-dimethylpyrrol-1-yl and dimethylamino peripheral groups is reported. Cross-coupling Suzuki-Miyaura reaction with phenylboronic acid was used to convert magnesium(II) porphyrazine with dimethylamino and 3,4-dibromo-2,5-dimethylpyrrol-1-yl groups to an analogue with bulky 2,5-dimethyl-3,4-diphenylpyrrol-1-yl moieties. Microwave-assisted organic synthesis approaches were used in the Paal-Knorr reaction leading to the modified diaminomaleonitrile intermediates and the Suzuki-Miyaura reaction, which allowed the obtaining of porphyrazine derivative. All compounds were characterized using UV–Vis, 1H and 13C NMR, including 2D techniques, as well as MS (ES or MALDI). An X-ray analysis of magnesium(II) porphyrazine with peripheral 3,4-dibromo-2,5-dimethylpyrrol-1-yl and dimethylamino substituents was also performed. The electrochemical properties of all obtained porphyrazine macrocycles were assessed using cyclic and differential pulse voltammetry. The susceptibility of new macrocycles to oxidation/reduction processes depended on the presence of halide substituents in their macrocyclic periphery. •Synthesis of porphyrazines with 3,4-dihalide-2,5-dimethylepyrrol-1-yl groups is reported.•Cross-coupling reaction was used to convert magnesium (II) porphyrazine to an analogue.•Microwave-assisted organic synthesis approaches were applied.•An X-ray analysis of magnesium (II) porphyrazine was performed.•The electrochemical properties of all obtained porphyrazine macrocycles were assessed.