Citation: Shuhong Wu, Wanying Han, Ying Wang, Yan Zhuang, Hui Niu, Lurong Li, Junhui Wang, Yuan Liu, Huan Lin, Kaifeng Wu, Jinni Shen, Yingguang Zhang, Michael K. H. Leung, Jinlin Long. Close π-π stacking facilitated intermolecular charge separation in self-assembled perylene monoimide for photocatalytic hydrogen production[J]. Chinese Journal of Structural Chemistry, ;2025, 44(6): 100592. doi: 10.1016/j.cjsc.2025.100592 shu

Close π-π stacking facilitated intermolecular charge separation in self-assembled perylene monoimide for photocatalytic hydrogen production

The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers, ultimately determining their photocatalytic performance. To achieve close π-π stacking, the suitable design of molecular structure is essential. Therefore, two isomers of pyridine carboxylic acid-modified perylene monoimide (PMI) were designed and synthesized, namely PM5A and PM6A. In aqueous solution, these molecules self-assemble into aggregates, which exhibit distinct stacking properties and optical characteristics. Upon photoexcitation, the loose π-π stacking of PM5A favors the generation of charge-transfer excitons (CTEs) over charge-separation excitons (CSEs). In contrast, PM6A, stabilized by intermolecular hydrogen bonds and possessing close π-π stacking, undergoes efficient charge separation (CS) to produce CSEs within 4.5 picoseconds. When incorporated into metal-insulator-semiconductor (MIS) photosystems with polyvinylpyrrolidone (PVP)-capped Pt, the Pt/PVP/PM6A system demonstrates a hydrogen evolution rate (HER) of 8100 μmol g^-1 h^-1, nearly five times higher than that of the Pt/PVP/PM5A system. Additionally, the maximum apparent quantum efficiency (AQE) reaches approximately 2.1% under irradiation with light of a single wavelength of λ = 425 nm.
- Photocatalysis,
- Hydrogen evolution,
- Supramolecular semiconductor,
- Perylene monoimide,
- π-π stacking
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