{"title":"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","authors":"Yan-Lin Li, Sheng-Li Huang, Guo-Yu Yang","doi":"10.1007/s11426-024-2043-2","DOIUrl":null,"url":null,"abstract":"<p>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 <b>(N^N)-I-COF</b>. <i>Via</i> imine-to-quinoline transformation and coordination anchorage of <b>Ru(N^N)</b><sub><b>3</b></sub> unit, <b>Ru(N^N)</b><sub><b>3</b></sub><b>@Q-COF</b> 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 H<sub>2</sub>O played a crucial role in the formation of reactive oxygen species (ROSs), which in turn influenced the olefin oxidation process. The hydrophilicity of <b>Ru(N^N)</b><sub><b>3</b></sub> facilitated the approach of H<sub>2</sub>O and O<sub>2</sub> to the photogenerated charges, thereby promoting ROSs generation. The lipophilicity of <b>Q-COF</b> allowed for the absorption of olefin substrates, and its nano-channels increased encountering possibility between olefins and ROSs. Consequently, <b>Ru(N^N)</b><sub><b>3</b></sub><b>@Q-COF</b> 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.</p>","PeriodicalId":772,"journal":{"name":"Science China Chemistry","volume":null,"pages":null},"PeriodicalIF":10.4000,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Engineering Ru(N^N)3-modified covalent organic framework for photocatalytic olefin epoxidation\",\"authors\":\"Yan-Lin Li, Sheng-Li Huang, Guo-Yu Yang\",\"doi\":\"10.1007/s11426-024-2043-2\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>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 <b>(N^N)-I-COF</b>. <i>Via</i> imine-to-quinoline transformation and coordination anchorage of <b>Ru(N^N)</b><sub><b>3</b></sub> unit, <b>Ru(N^N)</b><sub><b>3</b></sub><b>@Q-COF</b> 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 H<sub>2</sub>O played a crucial role in the formation of reactive oxygen species (ROSs), which in turn influenced the olefin oxidation process. The hydrophilicity of <b>Ru(N^N)</b><sub><b>3</b></sub> facilitated the approach of H<sub>2</sub>O and O<sub>2</sub> to the photogenerated charges, thereby promoting ROSs generation. The lipophilicity of <b>Q-COF</b> allowed for the absorption of olefin substrates, and its nano-channels increased encountering possibility between olefins and ROSs. Consequently, <b>Ru(N^N)</b><sub><b>3</b></sub><b>@Q-COF</b> 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.</p>\",\"PeriodicalId\":772,\"journal\":{\"name\":\"Science China Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":10.4000,\"publicationDate\":\"2024-09-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science China Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://doi.org/10.1007/s11426-024-2043-2\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science China Chemistry","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1007/s11426-024-2043-2","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Engineering Ru(N^N)3-modified covalent organic framework for photocatalytic olefin epoxidation
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.
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.
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