"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

J Am Chem Soc. 2016 Dec 14;138(49):15805-15808. doi: 10.1021/jacs.6b08620. Epub 2016 Dec 2.

Authors

Jingzhi Lu¹, Navneet S Khetrapal¹, Jacob A Johnson¹, Xiao Cheng Zeng¹, Jian Zhang¹

Affiliation

¹ Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.

PMID: 27960307
DOI: 10.1021/jacs.6b08620

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.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.
Research Support, Non-U.S. Gov't