Ru Metalloligands Participate in the Construction of POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reaction

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Inorganic Chemistry Pub Date : 2024-12-17 DOI:10.1021/acs.inorgchem.4c03064

Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Sen Liu, Pengtao Ma, Jingping Wang, Jingyang Niu

{"title":"Ru Metalloligands Participate in the Construction of POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reaction","authors":"Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Sen Liu, Pengtao Ma, Jingping Wang, Jingyang Niu","doi":"10.1021/acs.inorgchem.4c03064","DOIUrl":null,"url":null,"abstract":"Directed synthesis of high-efficiency visible photoinduced Baeyer–Villiger oxidation catalysts is of primary significance. Here, the isopolymolybdate anion [β-Mo8O26]4– is for the first time encapsulated with the photosensitive metalloligand [Ru(bpy)2(H2dcbpy)]2+ (bpy = 2,2′-bipyridine; H2dcbpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) to synthesize polyoxometalate@metal–organic frameworks, {(CdDMF)2[Ru(bpy)2(dcbpy)]3([β-Mo8O26])}·5DMF (Ru–Mo8). The composite photocatalyst Ru–Mo8 not only has a light absorption of 700 nm but also shortens the photogenerated electron transfer distances and accelerates charge and proton transfer. Ru–Mo8 can perform the Baeyer–Villiger oxidation with high selectivity and up to 96.7% yield under visible light (λ > 400 nm) irradiation. The turnover number and turnover frequency of the reaction were computed to be 967 and 548 h–1, respectively, and the apparent quantum yield was 6.84% by 425 nm. Simultaneously, the radical mechanism of Baeyer–Villiger oxidation of Ru–Mo8 in the O2/benzaldehyde system under visible light (λ > 400 nm) irradiation was proposed.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c03064","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

Directed synthesis of high-efficiency visible photoinduced Baeyer–Villiger oxidation catalysts is of primary significance. Here, the isopolymolybdate anion [β-Mo₈O₂₆]^4– is for the first time encapsulated with the photosensitive metalloligand [Ru(bpy)₂(H₂dcbpy)]²⁺ (bpy = 2,2′-bipyridine; H₂dcbpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) to synthesize polyoxometalate@metal–organic frameworks, {(CdDMF)₂[Ru(bpy)₂(dcbpy)]₃([β-Mo₈O₂₆])}·5DMF (Ru–Mo₈). The composite photocatalyst Ru–Mo₈ not only has a light absorption of 700 nm but also shortens the photogenerated electron transfer distances and accelerates charge and proton transfer. Ru–Mo₈ can perform the Baeyer–Villiger oxidation with high selectivity and up to 96.7% yield under visible light (λ > 400 nm) irradiation. The turnover number and turnover frequency of the reaction were computed to be 967 and 548 h^–1, respectively, and the apparent quantum yield was 6.84% by 425 nm. Simultaneously, the radical mechanism of Baeyer–Villiger oxidation of Ru–Mo₈ in the O₂/benzaldehyde system under visible light (λ > 400 nm) irradiation was proposed.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

Ru 金属配体参与构建 POM@MOF 以增强可见光诱导的拜尔-维利格氧化反应

定向合成高效可见光诱导Baeyer-Villiger氧化催化剂具有重要意义。在这里，异多酸阴离子[β-Mo8O26]4 -首次被光敏金属配体[Ru(bpy)2(H2dcbpy)]2+ (bpy = 2,2 ' -联吡啶包裹；H2dcbpy = 2,2′-联吡啶-5,5′-二羧酸)合成polyoxometalate@metal -有机骨架{(CdDMF)2[Ru(bpy)2(dcbpy)]3([β-Mo8O26])}·5DMF （Ru - mo8）。复合光催化剂Ru-Mo8不仅具有700 nm的光吸收，而且缩短了光生电子转移距离，加速了电荷和质子的转移。Ru-Mo8在可见光下具有高选择性的Baeyer-Villiger氧化反应，收率高达96.7% (λ >；400 nm)辐照。计算得到该反应的周转次数和周转频率分别为967和548 h-1，在425 nm处的表观量子产率为6.84%。同时，在可见光下O2/苯甲醛体系中Ru-Mo8 Baeyer-Villiger氧化的自由基机理(λ >；建议采用400 nm辐照。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.