Predicting the increase in electron affinity of phenoxy upon fluorination

0586913 - ÚFCH JH 2025 RIV NL eng J - Journal Article
Clarke, C. J. - Gibbard, J. A. - Brittain, W. D.G. - Verlet, Jan Raf Rogier
Predicting the increase in electron affinity of phenoxy upon fluorination.
Journal of Fluorine Chemistry. Roč. 277, JUL 2024 (2024), č. článku 110306. ISSN 0022-1139. E-ISSN 1873-3328
R&D Projects: GA MŠMT EH22_008/0004649
Grant - others:Ministerstvo školství, mládeže a tělovýchovy(CZ) CZ.02.01.01/00/22_008/0004649
Institutional support: RVO:61388955
Keywords : Anion photoelectron spectroscopy * Electron affinity * Fluorination * Fluorine chemistry * Phenoxy radical
OECD category: Physical chemistry
Impact factor: 1.9, year: 2022
Method of publishing: Open access

The site-specific fluorination of organic compounds can alter their electron affinity, EA, which in turn can be used to control their reactivity, physical properties, or binding affinities. Using anion photoelectron spectroscopy, we show that for the multiply fluorinated phenoxy radical, the change in EA is predominantly additive per fluorination and can be predicted by the simple formula: ΔEA = ∑iΔEAi − ΔEAC, where the numeric index i indicates the positions of fluorination. A small cooperative effect, ΔEAC, destabilizes the anion, but this only accounts for 11 % of the total ΔEA, in the extreme case of pentafluorophenolate. Our experimental results are consistent with those calculated using density functional theory, demonstrating the suitability of electronic structure calculations in the prediction of fluorination effects, for practical use in the synthetic design of organofluorines.
Permanent Link: https://hdl.handle.net/11104/0354283