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Communications in Science and TechnologyCommunications in Science and Technology

The oxidation of dipyrromethane by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) generally produces dipyrrin, but in the presence of trace water, a meso-hydroxy dipyrromethane can be formed. To investigate this unusual product, we then studied meso-hydroxy bis(p-anisoyl)-p-fluorophenyl dipyrromethane (3) obtained from the oxidation of bis(p-anisoyl)-p-fluorophenyl dipyrromethane (2). Spectroscopic studies (1H-NMR, UV-Vis, and fluorescence), mass spectrometry, and computational analyses were performed to investigate this mechanism. Zinc complexation of compound 3 altered the 1H-NMR spectrum and shifted the absorption peak from 325 nm to 567 nm with “turn-on fluorescence. Thermochemical studies have indicated that the formation of meso-hydroxy requires energy higher than dipyrrin. This study suggests that the electronic properties of meso-aryl and acyl groups are the key factors for the nucleophilic attack of water on cationic dipyrromethane intermediate. These results further improve the understanding of dipyrromethane oxidation pathways, which is crucial for the design and synthesis of dipyrrin-chemosensors.

This study successfully synthesized and characterized meso-hydroxy acyl dipyrromethane, revealing its unique spectroscopic properties and complexation behavior with zinc(II).The research demonstrated that dipyrrin is thermodynamically more stable than meso-hydroxy dipyrromethane, explaining the observed reaction pathways.Furthermore, computational analyses elucidated the role of substituent effects in modulating the formation of meso-hydroxy dipyrromethane during dipyrromethane oxidation.

Penelitian lebih lanjut dapat dilakukan untuk mengeksplorasi pengaruh variasi substituen pada posisi meso dan diasil terhadap stabilitas dan reaktivitas meso-hydroxy dipyrromethane. Hal ini dapat dilakukan dengan mensintesis serangkaian senyawa analog dengan substituen yang berbeda dan menganalisis sifat-sifatnya secara komprehensif. Selain itu, studi mendalam mengenai mekanisme kompleksasi antara meso-hydroxy dipyrromethane dengan ion logam transisi lainnya, seperti tembaga atau nikel, dapat membuka peluang pengembangan sensor ion logam baru dengan sensitivitas dan selektivitas yang lebih tinggi. Terakhir, penelitian dapat difokuskan pada aplikasi potensial meso-hydroxy dipyrromethane dan kompleks logamnya dalam bidang-bidang seperti fotokatalisis, terapi fotodinamik, atau sebagai bahan aktif dalam perangkat optoelektronik, dengan tujuan memanfaatkan sifat-sifat unik senyawa ini untuk menciptakan teknologi inovatif.

  1. Formation and stability investigation of meso-hydroxy diacyl-dipyrromethane | Communications in Science... doi.org/10.21924/cst.10.1.2025.1593Formation and stability investigation of meso hydroxy diacyl dipyrromethane Communications in Science doi 10 21924 cst 10 1 2025 1593
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