Direct spectroscopy of contact charge transfer states: Possible consequences for tryptophan excited-state deactivation pathways by O2 and formation of reactive oxygen species
Literature Information
Swen Siegert, Ferdinand Vogeler, Joachim Schiedt, Rainer Weinkauf
This paper demonstrates that photodetachment photoelectron spectroscopy (PD-PES) of non-covalently bound heteromolecular anion clusters allows direct access to neutral contact charge transfer (CCT) states. The 2,2′-bithiophene·indole cluster is investigated as a model system in such a way that both chromophores have similar optical excitation cross-sections and hence the PD-PES shows the signature of both molecules. For the complexes O2·stilbene, O2·indole and O2·N-methylindole the optical cross-sections of the conjugated chromophores are much larger than that of O2. This forces most of the anion-to-neutral photoexcitation into the CCT state. The CCT states lie below S1 for 2,2′-bithiophene·indole and O2·stilbene or even below T1 for O2·indole and O2·N-methylindole. Significant differences are found between the PD-PES of O2 with indole and N-methylindole indicating that different collision sites may have different CCT state energies and as a result different 1Δg oxygen formation efficiencies. We discuss the possible consequences of the energetics and the geometry changes for the excited-state deactivation of tryptophan via the CCT state O2−·tryptophan+.
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