Singlet Energy Transfer in Anthracene-Porphyrin Complexes: Mechanism, Geometry, and Implications for Intramolecular Photon Upconversion.

In this work we show that the mechanism for singlet excitation energy transfer (SET) in coordination complexes changes upon changing a single atom. SET is governed by two different mechanisms; Förster resonance energy transfer (FRET) based on Coulombic, through-space interactions, or Dexter energy transfer relying on exchange, through-bond interactions. On the basis of time-resolved fluorescence and transient absorption measurements, we conduct a mechanistic study of SET from a set of photoexcited anthracene donors to axially coordinated porphyrin acceptors, revealing the effect of coordination geometry and a very profound effect of the porphyrin central metal atom. We found that FRET is the dominating mechanism of SET for complexes with zinc-octaethylporphyrin (ZnOEP) as the acceptor, while Dexter energy transfer is the dominating mechanism of SET in a corresponding ruthenium complex (RuOEP). In addition, by analyzing the coordination geometry of the complexes and its temperature dependence, the binding angle potential energy of axially coordinated porphyrin complexes could be estimated. The results of this study are of fundamental importance and are discussed with respect to the consequences for developing intramolecular triplet-triplet annihilation photon upconversion in coordination complexes.