1. Efficient selective aerobic oxidation of sulfides by molecular dipole modulation in methylphosphate-substituted perylene diimide supramolecular polarization photocatalyst.
- Author
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Liu, Lin, Song, Ru, Wu, Yan, Song, Xiaoming, Song, Jiarui, Chen, Mo, Nie, Yina, Wang, Chengming, and Wan, Jun
- Subjects
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SUSTAINABLE chemistry , *PERYLENE , *SULFOXIDES , *SUSTAINABILITY , *DIMETHYL sulfide , *IMIDES - Abstract
Targeting the challenges of inadequate charge separation and insufficient molecular activation within the photocatalyst, we have successfully developed a novel supramolecular polarization photocatalyst with methylphosphate-substituted PDI (P-PDIP), which features a significant built-in electric field, resulting in substantial enhancements in both charge separation efficiency and molecule activation efficiency, thereby paving the way for an efficient and stable photocatalytic selective aerobic oxidation of sulfides. [Display omitted] • A novel P-PDIP supramolecular polarization photocatalyst is constructed for selective aerobic oxidation of sulfide. • A giant build-in electric field is produced in P-PDIP by molecular dipole modulation and polar molecular self-assembly. • The incorporation of methylphosphate groups improves the activation efficiency of O 2 and thioether molecules. • The P-PDIP achieves 99.9% conversion and 99.8% selectivity in the aerobic oxidation of methyl phenyl sulfide to sulfoxide. Photocatalytic aerobic oxidation is a promising sustainable strategy for the selective organic synthesis of industrially valuable chemicals. However, the poor charge separation and insufficient molecular activation restrict the overall photocatalytic efficiency. To address these issues, we have developed a novel approach involving molecular dipole modulation and polar molecular self-assembly to modulate the built-in electric field (BEF) in perylene diimide (PDI) supramolecular polarization photocatalysts by adjusting the electronegativity of terminal substituents. The optimized methylphosphate-substituted PDI (P-PDIP) supramolecular system features the strongest BEF induced by its large molecular dipole, with an intensity 3.89 times higher than that observed in methylcarboxy-substituted PDI (P-PDIC) and 5.64 times higher than that observed in P-PDI. This significant enhancement in BEF generates a powerful driving force within P-PDIP, facilitating directional charge separation toward active sites. Additionally, the incorporation of methylphosphate groups improves the activation efficiency of O 2 and thioether molecules, resulting in a remarkable photocatalytic performance for selective aerobic oxidation of sulfides into sulfoxide (up to 99.9% conversion and 99.8% selectivity). This study highlights that enhancing BEF through manipulating molecular dipoles can significantly improve photocatalytic activity, offering great potential for constructing efficient organic polarization photocatalysts in green chemistry and sustainable production. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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