“π-Hole−π” Interaction Promoted Photocatalytic Hydrodefluorination via Inner-Sphere Electron Transfer

Jingzhi Lu; Navneet S. Khetrapal; Jacob A. Johnson; Xiao Cheng Zeng; Jian Zhang

doi:10.1021/jacs.6b08620

“π-Hole−π” Interaction Promoted Photocatalytic Hydrodefluorination via Inner-Sphere Electron Transfer

Jingzhi Lu, Navneet S. Khetrapal, Jacob A. Johnson, Xiao Cheng Zeng, Jian Zhang

Research output: Contribution to journal › Article › peer-review

39 Scopus citations

Abstract

We describe a metal-free, photocatalytic hydrodefluorination (HDF) of polyfluoroarenes (FA) using pyrene-based photocatalysts (Py). The weak “π-hole−π” interaction between Py and FA promotes the electron transfer against unfavorable energetics (ΔG_ET up to 0.63 eV) and initiates the subsequent HDF. The steric hindrance of Py and FA largely dictates the HDF reaction rate, pointing to an inner-sphere electron transfer pathway. This work highlights the importance of the size and shape of the photocatalyst and the substrate in controlling the electron transfer mechanism and rates as well as the overall photocatalytic processes.

Original language	English (US)
Pages (from-to)	15805-15808
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	49
DOIs	https://doi.org/10.1021/jacs.6b08620
State	Published - Dec 14 2016

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "“π-Hole−π” Interaction Promoted Photocatalytic Hydrodefluorination via Inner-Sphere Electron Transfer",

abstract = "We describe a metal-free, photocatalytic hydrodefluorination (HDF) of polyfluoroarenes (FA) using pyrene-based photocatalysts (Py). The weak “π-hole−π” interaction between Py and FA promotes the electron transfer against unfavorable energetics (ΔGET up to 0.63 eV) and initiates the subsequent HDF. The steric hindrance of Py and FA largely dictates the HDF reaction rate, pointing to an inner-sphere electron transfer pathway. This work highlights the importance of the size and shape of the photocatalyst and the substrate in controlling the electron transfer mechanism and rates as well as the overall photocatalytic processes.",

author = "Jingzhi Lu and Khetrapal, {Navneet S.} and Johnson, {Jacob A.} and Zeng, {Xiao Cheng} and Jian Zhang",

note = "Funding Information: The authors acknowledge the support from the University of Nebraska?Lincoln. We also thank the Donors of the American Chemical Society Petroleum Research Fund (53678-DNI10) and National Science Foundation (DMR-1554918) for partial support of this research Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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AU - Lu, Jingzhi

AU - Khetrapal, Navneet S.

AU - Johnson, Jacob A.

AU - Zeng, Xiao Cheng

AU - Zhang, Jian

N1 - Funding Information: The authors acknowledge the support from the University of Nebraska?Lincoln. We also thank the Donors of the American Chemical Society Petroleum Research Fund (53678-DNI10) and National Science Foundation (DMR-1554918) for partial support of this research Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/12/14

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N2 - We describe a metal-free, photocatalytic hydrodefluorination (HDF) of polyfluoroarenes (FA) using pyrene-based photocatalysts (Py). The weak “π-hole−π” interaction between Py and FA promotes the electron transfer against unfavorable energetics (ΔGET up to 0.63 eV) and initiates the subsequent HDF. The steric hindrance of Py and FA largely dictates the HDF reaction rate, pointing to an inner-sphere electron transfer pathway. This work highlights the importance of the size and shape of the photocatalyst and the substrate in controlling the electron transfer mechanism and rates as well as the overall photocatalytic processes.

AB - We describe a metal-free, photocatalytic hydrodefluorination (HDF) of polyfluoroarenes (FA) using pyrene-based photocatalysts (Py). The weak “π-hole−π” interaction between Py and FA promotes the electron transfer against unfavorable energetics (ΔGET up to 0.63 eV) and initiates the subsequent HDF. The steric hindrance of Py and FA largely dictates the HDF reaction rate, pointing to an inner-sphere electron transfer pathway. This work highlights the importance of the size and shape of the photocatalyst and the substrate in controlling the electron transfer mechanism and rates as well as the overall photocatalytic processes.

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“π-Hole−π” Interaction Promoted Photocatalytic Hydrodefluorination via Inner-Sphere Electron Transfer

Abstract

ASJC Scopus subject areas

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