Skip to content

Solvent-dependent photochemical dynamics of a phenoxazine-based photoredox catalyst

Research output: Contribution to journalArticle

Original languageEnglish
JournalZeitschrift für Physikalische Chemie
DateAccepted/In press - 23 Mar 2020


Organic substitutes for ruthenium and iridium complexes are increasingly finding applications in chemical syntheses involving photoredox catalysis. However, the performance of these organic compounds as electron-transfer photocatalysts depends on their accessible photochemical pathways and excited state lifetimes. Here, the UV-induced dynamics of N-phenyl phenoxazine, chosen as a prototypical N-aryl phenoxazine organic photoredox catalyst, are explored in three solvents, N,N-dimethyl formamide, dichloromethane and toluene, using ultrafast transient absorption spectroscopy. Quantum chemistry calculations reveal the locally excited or charge-transfer electronic character of the excited states, and are used to assign the transient electronic and vibrational bands observed. In toluene-d8, complete ground-state recovery is (31 ± 3) % by internal conversion (IC) from the photo-excited state (or from S1 after IC but before complete vibrational relaxation), (13 ± 2) % via direct decay from vibrationally relaxed S1 (most likely radiative decay, with an estimated radiative lifetime of 13 ns) and (56 ± 3) % via the T1 state (with intersystem crossing (ISC) rate coefficient kISC = (3.3 ± 0.2) ± 108 s-1). In dichloromethane, we find evidence for excited state N-phenyl phenoxazine reaction with the solvent. Excited state lifetimes, ISC rates, and ground-state recovery show only modest variation with changes to the solvent environment because of the locally excited character of the S1 and T1 states.

    Structured keywords


    Research areas

  • photochemistry, transient absorption spectroscopy, ultrafast dynamics, organic photocatalyst



  • Full-text PDF (author’s accepted manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via Oldenbourg Verlag at [insert hyperlink] . Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 1.25 MB, PDF document

    Embargo ends: 1/01/99

    Request copy

View research connections

Related faculties, schools or groups