A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.
Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. 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), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis.
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Yang
Y
Jiao
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Wan-Lu
WL
Li
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Jiang-Fei
JF
Xu
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Guangtong
G
Wang
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Jun
J
Li
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Zhiqiang
Z
Wang
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, China. xi@mail.tsinghua.edu.cn.
Xi
X
Zhang
cucurbiturils; host-guest systems; radical cations; self-assembly; supramolecular chemistry