Triplet exciton fine structure in Pt-rich polymers studied by circularly polarized emission under high magnetic field

Incorporating heavy atoms into polymer chains represents an effective way to generate emissive triplets. Here we used magneto-optical emission spectroscopy up to 17.5 Tesla for studying the fine structure of the triplet exciton in a series of Pt-rich \ensuremath{\pi}-conjugated polymers with various intrachain Pt concentrations. We found that their phosphorescence emission band shows substantial field-induced circular polarization (FICPO) up to 50% with an unusual, nonmonotonic field dependence at cryogenic temperature. From the field-induced energy splitting between left and right circularly polarized phosphorescence we obtained the effective $g$ factor of triplet exciton varying in the range of $\ensuremath{-}0.13\text{\ensuremath{-}}0.85$, which depends on the Pt concentration in the polymer chains. The FICPO of triplet emission originates from the population difference in spin sublevels, which is determined by thermal equilibrium subjected to spin-orbit coupling (SOC), exchange, and Zeeman interactions. Surprisingly we also observed FICPO in the fluorescence emission that results from the singlet-triplet interaction caused by the strong SOC. From these results we extracted the various interaction parameters that describe the exciton fine structure in these Pt-contained compounds.