Xu Weiquan, Du Yinghao, Ma He, Tang Xingchen, Ou Qi, Xu Jiang-Fei, Zhang Xi
Key Lab of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, 100084, Beijing, China.
SINOPEC Research Institute of Petroleum Processing Co., Ltd, 100083, Beijing, China.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413129. doi: 10.1002/anie.202413129. Epub 2024 Oct 29.
Promoting the generation of triplet states is essential for developing efficient photocatalytic systems. This research presents a novel approach of host-stabilized through-space conjugation via the combination of covalent and non-covalent methods. The designed building block, 4,4'-(1,4(1,4)-dibenzene cyclohexaphane-1,4-diyl)bis(1-phenylpyridinium) chloride, features inherently stable through-space conjugation. When this block forms a 1 : 1 host-guest complex with cucurbit[8]uril, the through-space conjugation is further stabilized within the confined cavity. Both the generation and lifetime of triplet state are significantly increased, resulting from the host-stabilized through-space conjugation. Additionally, the ultrahigh binding constant of 6.58×10 M ensures the persistence of host-stabilization effect. As a result, the host-guest complex acts as a highly efficient catalyst in the photocatalytic oxidation of thioether and aromatic alcohol. In the photodegradation of lignin, a complex natural product, the host-guest complex also exhibits high efficiency, demonstrating its robustness. This line of research is anticipated to enrich the toolbox of supramolecular photochemistry and provide a strategy for fabricating efficient supramolecular photocatalysts.
促进三重态的产生对于开发高效光催化系统至关重要。本研究提出了一种通过共价和非共价方法相结合实现主体稳定的空间共轭的新方法。所设计的结构单元4,4'-(1,4(1,4)-二苯并环己六苯-1,4-二基)双(1-苯基吡啶鎓)氯化物具有固有的稳定空间共轭。当该结构单元与葫芦[8]脲形成1:1的主客体复合物时，空间共轭在受限腔内进一步稳定。由于主体稳定的空间共轭，三重态的产生和寿命均显著增加。此外，6.58×10 M的超高结合常数确保了主体稳定效应的持久性。因此，主客体复合物在硫醚和芳香醇的光催化氧化中作为高效催化剂。在木质素（一种复杂的天然产物）的光降解中，主客体复合物也表现出高效性，证明了其稳健性。预计这一系列研究将丰富超分子光化学的工具库，并为制备高效超分子光催化剂提供策略。
