超分子方法活化自由基:一种加速氧化反应的新策略
详细信息 查看官网全文
- 英文论文题名：Supramolecularly Activated Radical for Accelerated Catalytic Oxidation
- 论文作者：焦阳 ; 李婉璐 ; 徐江飞 ; 王广通 ; 李隽 ; 王治强 ; 张希
- 英文论文作者：Yang Jiao ; Wan-Lu Li ; Jiang-Fei Xu ; Guangtong Wang ; Jun Li ; Zhiqiang Wang ; Xi Zhang ; Department of Chemistry ; Tsinghua University
- 年：2016
- 作者机构：清华大学化学系有机光电子与分子工程教育部重点实验室;
- 论文关键词：超分子化学 ; 自由基 ; 芬顿氧化反应 ; 主客体相互作用
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第二十四分会：超分子组装与软物质材料
- 语种：中文
- 分类号：O641.3
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第二十四分会 ; 超分子组装与软物质材料
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：287k
- 原文格式：D
- 会议级别：全国
摘要
有机自由基是一类常见的反应中间体,调节其活性对于自由基反应而言至关重要。为此,我们提出了一种简单的超分子方法来活化自由基,以促进自由基反应的进行。以吡咯并吡咯二酮(DPP,一类常用的荧光染料分子)为例,它的芬顿氧化反应可分为两个阶段,其中关键的中间产物是DPP阳离子自由基。通过主客体相互作用,我们将葫芦[7]脲(CB[7]分子非共价结合在DPP自由基的两端,利用CB[7]分子内14个羰基的吸电子作用,实现对缺电子的DPP自由基的活化。研究表明,上述的超分子活化过程,引起了反应活化能的显著降低,进而使反应速率提升了42倍之多。这种超分子方法快捷、高效,只需要在水溶液中的简单混合即可完成,将有望成为加速自由基反应的一种新策略,也将为超分子催化体系的设计提供更为丰富的思路。
Tuning the activity of radicals is crucial for radical-mediated reactions. Herein, we develop a supramolecular strategy to accelerate Fenton reaction via the construction of supramolecularly activated radical. As a proof of the concept, cucurbit[7]uril(CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo-[3,4-c]-pyrrole(DPP), the model dye used for undergoing Fenton oxidation. DPP radical cation, the key intermediate in oxidation process, was activated due to the electron-withdrawing carbonyl groups of CB[7]. The activation induced a drastic decrease in apparent activation energy and greatly increased reaction rate. This facile supramolecular strategy is a promising methodology for facilitating radical reactions, which may enrich the realm of supramolecular catalysis.
Tuning the activity of radicals is crucial for radical-mediated reactions. Herein, we develop a supramolecular strategy to accelerate Fenton reaction via the construction of supramolecularly activated radical. As a proof of the concept, cucurbit[7]uril(CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo-[3,4-c]-pyrrole(DPP), the model dye used for undergoing Fenton oxidation. DPP radical cation, the key intermediate in oxidation process, was activated due to the electron-withdrawing carbonyl groups of CB[7]. The activation induced a drastic decrease in apparent activation energy and greatly increased reaction rate. This facile supramolecular strategy is a promising methodology for facilitating radical reactions, which may enrich the realm of supramolecular catalysis.
引文
[1]Jiao,Y.;Liu,K.;Wang,G.;Wang,Y.;Zhang X.Chem.Sci.2015,6:3975.