Comprehensive Insightsinto Exciplex Behavior in NonpolarMedia: Revisiting Weller’s Framework with Molecular Conformation

Exciplexes are pivotal in organic light-emitting diodes and photovoltaics. However, their formation and emission in nonpolar solvents remain unclear. Revisiting Weller’s works on photoinduced electron transfer (PET) rates and exciplex emission based on electrochemical redox potentials, we investigate exciplex behavior in cyclohexane using anthracene (Ant) as an acceptor and <i>N</i>,<i>N</i>-dimethylaniline (DMA) derivatives as donors. Employing steady-state and time-resolved spectroscopy, electrochemistry, and density functional theory (DFT) calculations, we demonstrate that electrochemical redox potentials alone inadequately explain the exciplex behavior in nonpolar environments. Our DFT analysis reveals that the C–N rotational angle of the dimethylamine group of a donor influences the highest occupied molecular orbital (HOMO) energy levels, affecting quenching processes. Furthermore, time-dependent DFT simulations accurately reproduce experimental exciplex emission spectra, linking emission intensity to donor contribution in the exciplex HOMO. These findings deepen the understanding of exciplex behavior in nonpolar media and provide insights for designing and interpreting exciplex-based optoelectronic materials.