Predicting the increase in electron affinity of phenoxy upon fluorination

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00586913" target="_blank" >RIV/61388955:_____/24:00586913 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0354283" target="_blank" >https://hdl.handle.net/11104/0354283</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jfluchem.2024.110306" target="_blank" >10.1016/j.jfluchem.2024.110306</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Predicting the increase in electron affinity of phenoxy upon fluorination

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Predicting the increase in electron affinity of phenoxy upon fluorination

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EH22_008%2F0004649" target="_blank" >EH22_008/0004649: Kvantové inženýrství a nanotechnologie</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Fluorine Chemistry

ISSN

0022-1139

e-ISSN

1873-3328

Svazek periodika

277

Číslo periodika v rámci svazku

JUL 2024

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

4

Strana od-do

110306

Kód UT WoS článku

001250070900001

EID výsledku v databázi Scopus

2-s2.0-85195055732