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使用卤化铅钙钛矿纳米晶体的能量转移光催化:敏化分子异构化和环加成反应

Energy-Transfer Photocatalysis Using Lead Halide Perovskite Nanocrystals: Sensitizing Molecular Isomerization and Cycloaddition.

作者信息

Liu Meng, Xia Pan, Zhao Guohui, Nie Chengming, Gao Kaimin, He Shan, Wang Lifeng, Wu Kaifeng

机构信息

State Key Laboratory of Molecular Reaction Dynamics, Dynamics Research Center for Energy and Environmental Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China.

University of the Chinese Academy of Sciences, Beijing, 100049, China.

出版信息

Angew Chem Int Ed Engl. 2022 Aug 26;61(35):e202208241. doi: 10.1002/anie.202208241. Epub 2022 Jul 19.

Abstract

A relatively new addition to the application portfolio of lead halide perovskites is to photosensitize molecular triplets for a variety of photochemical applications. Here we report visible-light-driven isomerization and cycloaddition of organic molecules sensitized by spectrally-tunable perovskite nanocrystals. We first demonstrate with stilbene as the substrate molecule that photoisomerization can proceed efficiently and rapidly by either directly grafting carboxylated stilbene onto nanocrystal surfaces or using triplet-acceptor ligands as the energy relay. The relay approach is more generally applicable as it does not require anchoring-group functionalization of substrate molecules, allowing us to facilely extend it to isomerization of a series of substituted stilbene molecules and ring-closing isomerization of diarylethene, as well as intermolecular [2+2] cycloaddition of acenaphthylene. This study opens an avenue of energy-transfer photocatalysis using perovskite nanocrystals.

摘要

卤化铅钙钛矿应用组合中一个相对较新的领域是使分子三线态光敏化,用于各种光化学应用。在此,我们报道了由光谱可调谐钙钛矿纳米晶体敏化的有机分子的可见光驱动异构化和环加成反应。我们首先以芪为底物分子证明,通过将羧基化芪直接接枝到纳米晶体表面或使用三线态受体配体作为能量中继,光异构化可以高效且快速地进行。中继方法更具普遍适用性,因为它不需要底物分子的锚定基团功能化,这使我们能够轻松地将其扩展到一系列取代芪分子的异构化、二芳基乙烯的闭环异构化以及苊烯的分子间[2+2]环加成反应。这项研究开辟了一条使用钙钛矿纳米晶体进行能量转移光催化的途径。

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