Figure 5.
Energy diagram illustrating photophysical processes leading to phosphorescence emission and quenching by oxygen (O2) and other diffusing quenchers (Qi). Absorption of a photon by an Oxyphor molecule, based on a Pt or Pd porphyrin,30 is followed by ultrafast S1→T1 intersystem crossing (isc) (kisc=1011-1013 s−1), yielding the triplet state (T1) with nearly unity efficiency. The subsequent T1→S0 phosphorescence is characterized by the rate constant kp, the inverse of the phosphorescence lifetime (1/τ0). The rate equation (1) can be integrated under quasi-stationary approximation, resulting in a single-exponential decay of the phosphorescence intensity I(t) (2), where the rate constant k is defined by the Stern-Volmer relationship (3).