{"title":"嵌有 N-羟基邻苯二甲酰亚胺的螺二芴基共轭微孔聚合物作为选择性溶剂依赖性有氧氧化的协同光催化剂","authors":"","doi":"10.1039/d4cy00296b","DOIUrl":null,"url":null,"abstract":"<div><p>The ideal catalytic oxidation system that uses the most environmentally benign reactants, such as molecular oxygen and natural light, and features sustainable heterogeneous characteristics, although long sought, has hardly been achieved. Herein, a spirobifluorene-based conjugated microporous polymer (CMP) covalently embedded with <em>N</em>-hydroxyphthalimide (NHPI) as a phthalimido <em>N</em>-oxyl (PINO) radical precursor was designed and synthesized. The as-synthesized porous <strong>CMP-NHPI</strong> leverages the spirobifluorene-based CMP as an exquisite photoredox platform to activate molecular oxygen for generating reactive oxygen species (ROS) and synergistically convert the embedded NHPI to an active PINO radical, thus establishing a fully green catalytic system. In particular, under visible light irradiation and air at ambient temperature, various primary aromatic alcohols can be highly selectively oxidized to their corresponding aldehydes or acids by switching the reaction solvent from acetonitrile to water. Control experiments and mechanistic studies reveal that the regulation of ROS in different solvents is responsible for the specific solvent-dependent oxidations.</p></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":null,"pages":null},"PeriodicalIF":4.4000,"publicationDate":"2024-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Spirobifluorene-based conjugated microporous polymer embedded with N-hydroxyphthalimide as a synergistic photocatalyst for selective solvent-dependent aerobic oxidations†\",\"authors\":\"\",\"doi\":\"10.1039/d4cy00296b\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The ideal catalytic oxidation system that uses the most environmentally benign reactants, such as molecular oxygen and natural light, and features sustainable heterogeneous characteristics, although long sought, has hardly been achieved. Herein, a spirobifluorene-based conjugated microporous polymer (CMP) covalently embedded with <em>N</em>-hydroxyphthalimide (NHPI) as a phthalimido <em>N</em>-oxyl (PINO) radical precursor was designed and synthesized. The as-synthesized porous <strong>CMP-NHPI</strong> leverages the spirobifluorene-based CMP as an exquisite photoredox platform to activate molecular oxygen for generating reactive oxygen species (ROS) and synergistically convert the embedded NHPI to an active PINO radical, thus establishing a fully green catalytic system. In particular, under visible light irradiation and air at ambient temperature, various primary aromatic alcohols can be highly selectively oxidized to their corresponding aldehydes or acids by switching the reaction solvent from acetonitrile to water. Control experiments and mechanistic studies reveal that the regulation of ROS in different solvents is responsible for the specific solvent-dependent oxidations.</p></div>\",\"PeriodicalId\":66,\"journal\":{\"name\":\"Catalysis Science & Technology\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2024-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysis Science & Technology\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2044475324003484\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Science & Technology","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2044475324003484","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Spirobifluorene-based conjugated microporous polymer embedded with N-hydroxyphthalimide as a synergistic photocatalyst for selective solvent-dependent aerobic oxidations†
The ideal catalytic oxidation system that uses the most environmentally benign reactants, such as molecular oxygen and natural light, and features sustainable heterogeneous characteristics, although long sought, has hardly been achieved. Herein, a spirobifluorene-based conjugated microporous polymer (CMP) covalently embedded with N-hydroxyphthalimide (NHPI) as a phthalimido N-oxyl (PINO) radical precursor was designed and synthesized. The as-synthesized porous CMP-NHPI leverages the spirobifluorene-based CMP as an exquisite photoredox platform to activate molecular oxygen for generating reactive oxygen species (ROS) and synergistically convert the embedded NHPI to an active PINO radical, thus establishing a fully green catalytic system. In particular, under visible light irradiation and air at ambient temperature, various primary aromatic alcohols can be highly selectively oxidized to their corresponding aldehydes or acids by switching the reaction solvent from acetonitrile to water. Control experiments and mechanistic studies reveal that the regulation of ROS in different solvents is responsible for the specific solvent-dependent oxidations.
期刊介绍:
A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis.
Editor-in-chief: Bert Weckhuysen
Impact factor: 5.0
Time to first decision (peer reviewed only): 31 days