W-band transient EPR and photoinduced absorption on spin-labeled fullerene derivatives

We investigated by W-band (94 GHz) transient electron paramagnetic resonance (TREPR) and photoinduced absorption (PIA) spectroscopy two fullerene derivatives bearing a nitroxide radical unit. After pulsed laser photoexcitation of the molecules in liquid toluene solution, complex EPR spectra are recorded, with lines in absorption and emission. The intrinsic higher spectral and temporal resolution of the W-band frequency leads to the assignment of all the lines in the spectrum and the determination of the sign and the absolute value of the exchange coupling between the fullerene in its photoexcited triplet state (ST = 1) and the radical (SR = 1/2). The two compounds with different fullerene–nitroxide spacers show opposite—ferromagnetic and antiferromagnetic—exchange couplings. The time evolution of the spectra and the polarization of the lines are interpreted in terms of several possible spin polarization mechanisms. The EPR measurements are complemented with PIA experiments.