Shao Jingjing, Wang He, Tao Xin, Zhu Guangshan
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University Changchun 130024 China
Chem Sci. 2025 Jun 23. doi: 10.1039/d5sc00394f.
Porous aromatic frameworks (PAFs) are considered as promising photocatalysts for efficient organic transformations. In this study, the synthesis of donor-acceptor (D-A)-type hexaazatrinaphthylene-based porous aromatic frameworks (HATN-PAFs) is presented. By linking HATN units with other different fragments, the surface areas, bandgaps, energy levels and photoelectric properties of HATN-PAFs could be easily tuned. Notably, the combination of HATN with triphenylamine (TPA) fragments facilitates photoinduced charge separation and migration, and reactant transport and activation during photocatalysis, which achieves high yields (up to 99%), an expandable substrate scope (20 examples), and good recyclability (up to 10 cycles) for the photosynthesis of 2-benzothiazoles under an air atmosphere upon excitation by a blue LED light (460 nm, 24 W). This photocatalytic system does not require additional oxidants or metals, making it environmentally friendly. A mechanistic study reveals that the simultaneous generation of the reactive oxygen species O˙ and O over this catalytic system may jointly accelerate the oxidative formation of 2-benzothiazoles.
多孔芳香框架材料（PAFs）被认为是用于高效有机转化的有前景的光催化剂。在本研究中，介绍了基于给体-受体（D-A）型六氮杂三亚萘的多孔芳香框架材料（HATN-PAFs）的合成。通过将HATN单元与其他不同片段相连，HATN-PAFs的表面积、带隙、能级和光电性能可以很容易地调节。值得注意的是，HATN与三苯胺（TPA）片段的结合促进了光催化过程中的光生电荷分离和迁移，以及反应物的传输和活化，在蓝色LED灯（460 nm，24 W）激发下，在空气气氛中实现了2-苯并噻唑光合成的高产率（高达99%）、可扩展的底物范围（20个实例）和良好的可循环性（高达10次循环）。该光催化体系不需要额外的氧化剂或金属，具有环境友好性。机理研究表明，在该催化体系上同时生成活性氧物种O˙和O可能共同加速2-苯并噻唑的氧化形成。
