Circularly polarized photoluminescence from platinum porphyrins in organic hosts: Magnetic field and temperature dependence

We study the temperature and magnetic field-dependent photoluminescence from the metalorganic molecules octaethyl-porphine platinum (PtOEP) and porphine platinum (PtP) that are doped into organic hosts. We first consider PtOEP in the polymer host poly-dioctylfluorene (PFO), which is characteristic of the phosphorescent dopants and polymers used in organic light-emitting diodes. We observe that the intensity of the PtOEP zero-phonon emission band, which is strongly suppressed at low temperatures to 1.6 K, increases dramatically with applied magnetic field and is accompanied by a marked circular polarization. This “magnetic brightening” effect, similar to that observed in other organic systems such as carbon nanotubes, highlights the interplay between low-energy optically active and optically forbidden excited states of PtOEP, which become mixed in applied magnetic fields. To elucidate these findings, we also investigate (i) dilute PtOEP in n-octane hosts (where emission lines are much sharper), and (ii) dilute PtP in n-octane hosts, for which the emission spectra are simpler and can be directly compared with theory. Detailed electronic structure calculations of PtP were performed, and a model for the magnetic field and temperature dependence of the zero phonon emission lines is developed, which agrees quantitatively with the data for PtP and with the circular polarization of the PtOEP emission.