Engineering Ru(N^N)3-modified covalent organic framework for photocatalytic olefin epoxidation

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Science China Chemistry Pub Date : 2024-09-10 DOI:10.1007/s11426-024-2043-2

Yan-Lin Li, Sheng-Li Huang, Guo-Yu Yang

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Abstract

Photocatalytic olefin oxidation using air as an oxidant is an environmentally friendly method for producing epoxides. Covalent organic frameworks (COFs) have emerged as promising photocatalysts in various organic synthesis reactions. The combination of tri-(2-pyridinal aldehyde)-containing precursor with 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)trianiline generated (N^N)-I-COF. Via imine-to-quinoline transformation and coordination anchorage of Ru(N^N)₃ unit, Ru(N^N)₃@Q-COF was obtained with improved chemical stability, skeleton conjugation, and novel photochemical characteristics, and demonstrated excellent photocatalytic activity in olefin epoxidation with a wide range of substrates. The presence of H₂O played a crucial role in the formation of reactive oxygen species (ROSs), which in turn influenced the olefin oxidation process. The hydrophilicity of Ru(N^N)₃ facilitated the approach of H₂O and O₂ to the photogenerated charges, thereby promoting ROSs generation. The lipophilicity of Q-COF allowed for the absorption of olefin substrates, and its nano-channels increased encountering possibility between olefins and ROSs. Consequently, Ru(N^N)₃@Q-COF provided an intriguing platform for olefin photooxidation and could be recycled multiple times without any degradation in performance. This report revealed that the conversion of classical ROSs into less potent oxidants with rapid kinetic rates played a crucial role in achieving highly efficient and selective epoxidation of terminal olefins.

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用于光催化烯烃环氧化的 Ru(N^N)3 改性共价有机框架工程设计

使用空气作为氧化剂进行光催化烯烃氧化是一种生产环氧化物的环保方法。在各种有机合成反应中，共价有机框架（COFs）已成为前景广阔的光催化剂。将含三(2-吡啶醛)的前体与 4,4′,4″-(1,3,5-三嗪-2,4,6-三基)三苯胺结合生成 (N^N)-I-COF 。通过亚胺到喹啉的转化和 Ru(N^N)3 单元的配位锚定，Ru(N^N)3@Q-COF 获得了更好的化学稳定性、骨架共轭性和新颖的光化学性质，并在多种底物的烯烃环氧化反应中表现出优异的光催化活性。H2O 的存在对活性氧（ROS）的形成起到了关键作用，而活性氧的形成又反过来影响了烯烃的氧化过程。Ru(N^N)3 的亲水性有利于 H2O 和 O2 接近光生电荷，从而促进 ROSs 的生成。Q-COF 的亲油性允许吸收烯烃基质，其纳米通道增加了烯烃和 ROS 之间相遇的可能性。因此，Ru(N^N)3@Q-COF 为烯烃光氧化提供了一个有趣的平台，并且可以多次循环使用而不会降低性能。该报告揭示了将传统的 ROS 转化为具有快速动力学速率的低效氧化剂在实现末端烯烃的高效和选择性环氧化中起着至关重要的作用。

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.