Multifaceted Interactions of Thermally Activated Delayed Fluorescent Emitters with Dielectric Environments: Charge Transfer vs. Structural Relaxation

Thermally activated delayed fluorescence (TADF) emitters doped in host–guest systems are widely utilized for organic light-emitting diodes (OLEDs), where key rate constants and the fluorescence quantum yield (ΦF) are strongly influenced by the surrounding environment. However, the multifaceted interactions, i.e., dipole–dipole interaction and conformational restraint between the emitter and environment have been rarely investigated systematically, where excited state charge transfer (CT) and structural relaxation (SR) of emitters should be considered equally. In this study, four representative CT–TADF emitters were selected as model systems and studied in PS/PMMA:TADF:CA host–guest doped films with varied dielectric constants and matrix rigidity. Within D–A and D–A–D configurations, donor substitution from PXZ to DMAC varied CT characteristics, whereas TRZ-based D–A and DPS-based D–A–D emitters provided a relative difference in SR owing to their different rigidity. The total reorganization energy (λTotal) was introduced as a quantitative measure of these multifaceted interactions and correlated with the rate constants. The results indicate that the dielectric dependence of the nonradiative decay rate (knrS) for D–A–D molecules cannot be explained by the simplified energy gap law, where the vibronic effect plays the role of a game changer. This work provides a quantitative framework and highlights vibrational frequency as a key design parameter for optimizing ΦF in host–guest doped OLED devices.