{"title":"双使能光响应镉-有机骨架的Knoevenagel缩合和烯烃全氟烷基化反应","authors":"Nana Yuan , Jia Cao , Yixia Ren , Xiufang Hou , Sanping Chen","doi":"10.1039/d5gc01928a","DOIUrl":null,"url":null,"abstract":"<div><div>In this paper, a 3D porous cadmium–organic framework, named [Cd(DDB)<sub>0.5</sub>(4,4′-bimp)<sub>0.5</sub>(H<sub>2</sub>O)]·H<sub>2</sub>O (Cd-MOF), was synthesized by hydrothermal synthesis using cadmium acetate (Cd(Ac)<sub>2</sub>·2H<sub>2</sub>O), 1,4-di(3,5-dicarboxyphenoxy)benzene (H<sub>4</sub>DDB) and 4,4-bis (imidazole-1-ylmethyl)biphenyl (4,4′-bimp) as raw materials. The colorless flake-like crystal of Cd-MOF is a 4,4′-bimp-pillared framework based on a 2D network from DDB linked with the dinuclear Cd2 unit. This non-precious metal material exhibits relatively wide light absorption, excellent thermal stability, high cycle recyclability, and a mesoporous specific surface area. Under the excitation of a blue LED (450 nm) light source, the dual photocatalytic activity of the Cd-MOF was realized: the photocatalytic Knoevenagel condensation reaction of aldehydes and malononitrile (yield up to 67–97.6%) and an efficient light-driven olefin-perfluoroalkyl iodide atom transfer radical addition reaction (yield reached 51–94.8%), achieving a “two birds with one stone” effect. Control experiments and theoretical calculations support our proposed radical mechanism. These reactions feature broad substrate applicability, good functional group tolerance and mild conditions. This work broadens the application of MOF-based materials in the field of photocatalysis and provides new ideas for sustainable green organic synthesis in the future.</div></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":"27 28","pages":"Pages 8603-8612"},"PeriodicalIF":9.2000,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Dual enabling photomediated Knoevenagel condensation and alkene perfluoroalkylation reactions by a photoresponsive cadmium–organic framework†\",\"authors\":\"Nana Yuan , Jia Cao , Yixia Ren , Xiufang Hou , Sanping Chen\",\"doi\":\"10.1039/d5gc01928a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>In this paper, a 3D porous cadmium–organic framework, named [Cd(DDB)<sub>0.5</sub>(4,4′-bimp)<sub>0.5</sub>(H<sub>2</sub>O)]·H<sub>2</sub>O (Cd-MOF), was synthesized by hydrothermal synthesis using cadmium acetate (Cd(Ac)<sub>2</sub>·2H<sub>2</sub>O), 1,4-di(3,5-dicarboxyphenoxy)benzene (H<sub>4</sub>DDB) and 4,4-bis (imidazole-1-ylmethyl)biphenyl (4,4′-bimp) as raw materials. The colorless flake-like crystal of Cd-MOF is a 4,4′-bimp-pillared framework based on a 2D network from DDB linked with the dinuclear Cd2 unit. This non-precious metal material exhibits relatively wide light absorption, excellent thermal stability, high cycle recyclability, and a mesoporous specific surface area. Under the excitation of a blue LED (450 nm) light source, the dual photocatalytic activity of the Cd-MOF was realized: the photocatalytic Knoevenagel condensation reaction of aldehydes and malononitrile (yield up to 67–97.6%) and an efficient light-driven olefin-perfluoroalkyl iodide atom transfer radical addition reaction (yield reached 51–94.8%), achieving a “two birds with one stone” effect. Control experiments and theoretical calculations support our proposed radical mechanism. These reactions feature broad substrate applicability, good functional group tolerance and mild conditions. This work broadens the application of MOF-based materials in the field of photocatalysis and provides new ideas for sustainable green organic synthesis in the future.</div></div>\",\"PeriodicalId\":78,\"journal\":{\"name\":\"Green Chemistry\",\"volume\":\"27 28\",\"pages\":\"Pages 8603-8612\"},\"PeriodicalIF\":9.2000,\"publicationDate\":\"2025-04-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Green Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1463926225005321\",\"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":"Green Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1463926225005321","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Dual enabling photomediated Knoevenagel condensation and alkene perfluoroalkylation reactions by a photoresponsive cadmium–organic framework†
In this paper, a 3D porous cadmium–organic framework, named [Cd(DDB)0.5(4,4′-bimp)0.5(H2O)]·H2O (Cd-MOF), was synthesized by hydrothermal synthesis using cadmium acetate (Cd(Ac)2·2H2O), 1,4-di(3,5-dicarboxyphenoxy)benzene (H4DDB) and 4,4-bis (imidazole-1-ylmethyl)biphenyl (4,4′-bimp) as raw materials. The colorless flake-like crystal of Cd-MOF is a 4,4′-bimp-pillared framework based on a 2D network from DDB linked with the dinuclear Cd2 unit. This non-precious metal material exhibits relatively wide light absorption, excellent thermal stability, high cycle recyclability, and a mesoporous specific surface area. Under the excitation of a blue LED (450 nm) light source, the dual photocatalytic activity of the Cd-MOF was realized: the photocatalytic Knoevenagel condensation reaction of aldehydes and malononitrile (yield up to 67–97.6%) and an efficient light-driven olefin-perfluoroalkyl iodide atom transfer radical addition reaction (yield reached 51–94.8%), achieving a “two birds with one stone” effect. Control experiments and theoretical calculations support our proposed radical mechanism. These reactions feature broad substrate applicability, good functional group tolerance and mild conditions. This work broadens the application of MOF-based materials in the field of photocatalysis and provides new ideas for sustainable green organic synthesis in the future.
期刊介绍:
Green Chemistry is a journal that provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998), which defines green chemistry as the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry aims to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The journal welcomes submissions on all aspects of research relating to this endeavor and publishes original and significant cutting-edge research that is likely to be of wide general appeal. For a work to be published, it must present a significant advance in green chemistry, including a comparison with existing methods and a demonstration of advantages over those methods.