Abstract

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.
Original languageEnglish
JournalZeitschrift für Physikalische Chemie
Early online date9 Jun 2020
DOIs
Publication statusE-pub ahead of print - 9 Jun 2020

Structured keywords

  • BCS and TECS CDTs

Keywords

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

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