Magnesium(II) porphyrazine with peripherally overloaded pyrrolyl substituents – Synthesis, optical and electrochemical characterization

• Published in: Journal of molecular structure 2024-12, Vol.1318, p.139356, Article 139356
• Main Authors: Szczolko, Wojciech, Koczorowski, Tomasz, Bakun, Pawel, Kryjewski, Michal, Grajewski, Mateusz, Popenda, Lukasz, Goslinski, Tomasz
• Format: Article
• Language: English
• Subjects: Diaminomaleonitrile; Electrochemistry; Macrocyclization reaction; Microwave assisted organic synthesis; Porphyrazine
• ISSN: 0022-2860
• DOI: 10.1016/j.molstruc.2024.139356

•MAOS approach was applied in the cross-coupling reactions leading to porphyrazines.•MAOS approach was used in the Paal-Knorr reaction towards diaminomaleonitriles.•Optical and electrochemical properties of porphyrazines were assessed. Cross-coupling Suzuki-Miyaura reaction using Microwave Assisted Organic Synthesis (MAOS) approach of phenylboronic acid and magnesium(II) porphyrazines with peripheral dimethylamino and 3,4-dibromo-2,5-diphenylpyrrol-1-yl or 3-bromo-2,4,5-triphenylpyrrol-1-yl groups led to magnesium(II) porphyrazines with dimethylamino and 2,3,4,5-tetraphenylpyrrol-1-yl groups. MAOS approach was also used in the Paal-Knorr reaction to synthesise the modified diaminomaleonitrile intermediates. All intermediates and macrocycles were characterized using UV-Vis, 1H and 13C NMR spectroscopy, as well as ES or MALDI MS spectrometry. The optical and electrochemical properties of obtained porphyrazine macrocycles were assessed. It was found that the susceptibility of new macrocycles to oxidation/reduction processes analyzed by cyclic and differential pulse voltammetry depended on the presence of bromide and the number of phenyl substituents in the macrocyclic periphery.