Unprecedented Bifunctional Chemistry of Bis(acyl)phosphane Oxides in Aqueous and Alcoholic Media

Max Schmallegger, Anna Eibel, Jan P. Menzel, Anne Marie Kelterer, Michal Zalibera, Christopher Barner-Kowollik, Hansjörg Grützmacher, Georg Gescheidt

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Tailor-made photoinitiators play an important role for efficient radical polymerisations in aqueous media, especially in hydrogel manufacturing. Bis(acyl)phosphane oxides (BAPOs) are among the most active initiators. Herein, we show that they display a remarkable photochemistry in aqueous and alcoholic media: Photolysis of BAPOs in the presence of water or alcohols provides a new delocalized π-radical, which does not participate in the polymerization. It either converts into a monoacylphosphane oxide acting as a secondary photoactive species or it works as a one-electron reducing agent. Upon the electron-transfer process, it again produces a dormant photoinitiator. We have established the structure and the chemistry of this π radical using steady-state and time-resolved (CIDEP) EPR together with ESI-MS, NMR spectroscopy, and DFT calculations. Our results show that bis(acyl)phosphane oxides act as bifunctional reagents when applied in aqueous and alcoholic media.

Original languageEnglish
Pages (from-to)8982-8986
Number of pages5
JournalChemistry - a European Journal
Volume25
Issue number38
DOIs
Publication statusPublished - 5 Jul 2019

Fingerprint

phosphine
Oxides
Cross-Linking Reagents
Electrons
Photochemical reactions
Hydrogel
Reducing Agents
Photolysis
Reducing agents
Free radical polymerization
Hydrogels
Discrete Fourier transforms
Nuclear magnetic resonance spectroscopy
Paramagnetic resonance
Alcohols
Polymerization
Water

Keywords

  • BAPOs
  • density functional calculations
  • ESI-MS
  • NMR spectroscopy
  • photochemistry

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Unprecedented Bifunctional Chemistry of Bis(acyl)phosphane Oxides in Aqueous and Alcoholic Media. / Schmallegger, Max; Eibel, Anna; Menzel, Jan P.; Kelterer, Anne Marie; Zalibera, Michal; Barner-Kowollik, Christopher; Grützmacher, Hansjörg; Gescheidt, Georg.

In: Chemistry - a European Journal, Vol. 25, No. 38, 05.07.2019, p. 8982-8986.

Research output: Contribution to journalArticleResearchpeer-review

Schmallegger, Max ; Eibel, Anna ; Menzel, Jan P. ; Kelterer, Anne Marie ; Zalibera, Michal ; Barner-Kowollik, Christopher ; Grützmacher, Hansjörg ; Gescheidt, Georg. / Unprecedented Bifunctional Chemistry of Bis(acyl)phosphane Oxides in Aqueous and Alcoholic Media. In: Chemistry - a European Journal. 2019 ; Vol. 25, No. 38. pp. 8982-8986.
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