Temporal Dynamics of Solid-State Thermally Activated Delayed Fluorescence: Disorder or Ultraslow Solvation?

Time-resolved emission spectra of thermally activated delayed fluorescence (TADF) compounds in solid hosts demonstrate significant temporal shifts. To explain the shifts, two possible mechanisms were suggested, namely, slow solid-state solvation and conformational disorder. Here we employ solid hosts with controllable polarity for analysis of the temporal dynamics of TADF. We show that temporal fluorescence shifts are independent of the dielectric constant of the solid film; however, these shifts evidently depend on the structural parameters of both the host and the TADF dopant. A ≤50% smaller emission peak shift was observed in more rigid polymer host polystyrene than in poly(methyl methacrylate). The obtained results imply that both the host and the dopant should be as rigid as possible to minimize fluorescence instability.