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 (ΔGETup 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.
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors.forename: Jingzhi
authors.initials: J
authors.lastname: Lu
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors.forename: Navneet S
authors.initials: NS
authors.lastname: Khetrapal
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors.forename: Jacob A
authors.initials: JA
authors.lastname: Johnson
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors.forename: Xiao Cheng
authors.initials: XC
authors.lastname: Zeng
authors.affiliation: Department of Chemistry, University of Nebraska-Lincoln , Lincoln, Nebraska 68588, United States.
authors.forename: Jian
authors.initials: J
authors.lastname: Zhang