Tang Bohan, Xu Weiquan, Xu Jiang-Fei, Zhang Xi
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Angew Chem Int Ed Engl. 2021 Apr 19;60(17):9384-9388. doi: 10.1002/anie.202100185. Epub 2021 Mar 17.
The development of non-covalent synthetic strategy to fabricate efficient photocatalysts is of great importance in theranostic and organic materials. Herein, a fluorochrome N,N'-dimethyl 2,5-bis(4-pyridinium)thiazolo[5,4-d]thiazolediiodide (MPT) was transformed into an efficient photocatalyst through supramolecular dimerization in the cavity of cucurbit[8]uril (CB[8]). The host-enhanced charge transfer interaction within the supramolecular dimer 2MPT-CB[8] dramatically promoted intersystem crossing to produce triplet. In addition, the staggered conformation of 2MPT-CB[8] facilitated the energy transfer and electron transfer of the triplet. As a result, 2MPT-CB[8] could serve as a high-efficiency photocatalyst for the oxidative hydroxylation of arylboronic acids. This supramolecular dimerization strategy enriches the supramolecular engineering of functional π-systems. It is anticipated that this strategy can be extended to fabricate various π-systems with tailor-made functions.
开发用于制备高效光催化剂的非共价合成策略在诊疗与有机材料领域具有重要意义。在此，一种荧光染料N,N'-二甲基2,5-双(4-吡啶基)噻唑并[5,4-d]噻唑二碘化物(MPT)通过在葫芦[8]脲(CB[8])空腔内的超分子二聚作用转化为一种高效光催化剂。超分子二聚体2MPT-CB[8]内的主体增强电荷转移相互作用显著促进了系间窜越以产生三重态。此外，2MPT-CB[8]的交错构象促进了三重态的能量转移和电子转移。结果，2MPT-CB[8]可作为芳基硼酸氧化羟基化反应的高效光催化剂。这种超分子二聚策略丰富了功能性π体系的超分子工程。预计该策略可扩展用于制备具有定制功能的各种π体系。
