Influence of C60 Aggregation on Pseudorotation in the Excited Triplet State Probed by Multifrequency Time-Resolved EPR

The influence of C₆₀ aggregation on time-resolved (TR) electron paramagnetic resonance (EPR) of C₆₀ in the excited triplet state was investigated by multifrequency EPR techniques. Temperature-independent X-band (9.7 GHz) TR-EPR spectra were observed in a fresh toluene solution, while temperature-dependent ones were reported in literatures. The experimental spectra in this study indicated that the pseudorotation of pristine C₆₀ in frozen toluene solution is not frozen out even at lower temperatures. Careful investigations of TR-EPR and its decay kinetics demonstrated that the pseudorotation can be affected by C₆₀ aggregation. A comparison between X- and W-band (94.9 GHz) results indicated that the aggregation can be accelerated by a capillary effect. Three decay constants were extracted from the analysis of the decay kinetics. The fastest component was ascribed to the pseudorotation, which was independent of temperature in the range of 10–40 K. The temperature dependences of the decay kinetics showed that the pseudorotation is not affected by C₆₀ aggregation at higher temperatures.