Peptoid-Conjugated Magnetic Field-Sensitive Exciplex System at High and Low Solvent Polarities

The magnetic field effect (MFE) in exciplex emission (ExE) has been studied for decades, but it has been observed to occur only in solvents with a limited range of polarity. This limitation is mainly due to the reversible interconversion collapse between two quenching products of the photoinduced electron transfer, the exciplex and magnetic field-sensitive radical ion pair (RIP) beyond that polarity range. In a nonpolar solvent, the formation of RIPs is suppressed, whereas in a polar solvent, the probability of their re-encounter forming the exciplexes decreases. In this study, we developed new exciplex-forming (phenylphenanthrene)-(phenyl-N,N-dimethylaniline)-peptoid conjugates (PhD-PCs) to overcome this limitation. The well-defined peptoid structure allows precise control of the distance and the relative orientation between two conjugated moieties. Steady-state and time-resolved spectroscopic data indicate that the PhD-PCs can maintain the reversibility, which allows MFEs in ExE regardless of the solvent polarity. Subtle differences between the ExEs of the PhD-PCs were observed and explained by their exciplex geometries obtained through time-dependent density functional theory (TD-DFT) calculations.