The reduction potential of diphenyliodonium polymerisation photoinitiator is not −0.2 V vs. SCE. A computational study
Authors:
- Piotr P. Romańczyk,
- Stefan S. Kurek
Abstract
The accurate potentials of Ph2I+ cation reduction, yielding in one step Ph• and PhI, are equal to -0.68, -0.61 and -0.67 V vs. SCE, in MeCN, DMF and water, respectively, according to state-of-the-art quantum chemical calculations using the benchmark gas-phase energetics (the C-I bond homolytic dissociation energy in Ph2I+ and electron affinity of PhI•+) from the explicitly correlated coupled-cluster method (CCSD(T)-F12) together with the SMD solvation free energies. The alkyl (Me or t-Bu) substitution effect on the reduction potential of Ph2I+ was estimated to be less than 50 mV. It was demonstrated that employing the ubiquitously used erroneous E°(Ph2I+) value of -0.2 V in the prediction of DeltaG° for photoinduced electron transfer may lead to failed photoinitiated polymerisation experiments.
- Record ID
- CUT398be0cc9f89434eb62fc3a9a1f56f5d
- Publication categories
- ;
- Author
- Journal series
- Electrochimica Acta, ISSN 0013-4686, e-ISSN 1873-3859
- Issue year
- 2017
- Vol
- 255
- Pages
- 482-485
- Other elements of collation
- rys.; tab.; Bibliografia (na s.) - 484-485; Bibliografia (liczba pozycji) - 33; Oznaczenie streszczenia - Abstr.; Numeracja w czasopiśmie - Vol. 255
- Keywords in English
- diaryliodonium cation, redox potential calculation, dissociative electron transfer, coupled cluster calculations, DFT calculations
- DOI
- DOI:10.1016/j.electacta.2017.09.166 Opening in a new tab
- URL
- http://www.sciencedirect.com/science/article/pii/S0013468617320376 Opening in a new tab
- Language
- eng (en) English
- Score (nominal)
- 40
- Additional fields
- Indeksowana w: Web of Science, Scopus
- Uniform Resource Identifier
- https://cris.pk.edu.pl/info/article/CUT398be0cc9f89434eb62fc3a9a1f56f5d/
- URN
urn:pkr-prod:CUT398be0cc9f89434eb62fc3a9a1f56f5d
* presented citation count is obtained through Internet information analysis, and it is close to the number calculated by the Publish or PerishOpening in a new tab system.