Oxygen sensing based on lifetime of photoexcited triplet state of platinum porphyrin-polystyrene film using time-resolved spectroscopy

Abstract

Optical oxygen-sensing systems based on the quenching of the photoexcited triplet state of platinum porphyrins—platinum octaethylporphyrin (PtOEP) and platinum tetrakis(pentafluorophenyl)porphyrin (PtTFPP)—in polystyrene (PS) using two different time-resolved spectroscopies (luminescence lifetime measurement and diffuse reflectance laser flash photolysis) have been developed. Using both spectroscopies, the same values of Stern-Volmer constant KSV and quenching rate constant kq (KSV = kqτ0) are obtained. The decays of the luminescence and triplet-triplet reflectance of the platinum porphyrins in PS consisted of two components (faster and slower lifetimes) in the absence and presence of oxygen. For both faster and slower components the lifetime decreases with increasing oxygen concentration. For both components a Stern-Volmer plot of the platinum porphyrin-PS films exhibits linearity. However, kq of the faster component is larger than that of the slower component (for PtOEP, three times larger; for PtTFPP, 40 times larger), indicating that two different oxygen-accessible sites exist in the platinum porphyrin-PS films. The faster and slower components are related to oxygen-accessible sites on the surface and in the bulk of the platinum porphyrin films respectively. Concerning the fractional contributions of each lifetime component, the contribution of the faster component is greater than that of the slower component, indicating that the sensing site on the surface is important for optical sensing. The contribution of different oxygen-accessible sites in platinum porphyrin-PS films for oxygen sensing is clarified by these techniques.