Temperature-dependent dynamics of endohedral fullerene Sc₂@C₈₀(CH₂Ph) studied by EPR spectroscopy

Endohedral fullerenes are promising materials for the quantum information and quantum processing due to the unique properties of the electron-nuclear spin system well isolated from the environment inside the fullerene cage. The endofullerene Sc₂@C₈₀(CH₂Ph) features a strong hyperfine interaction between one electron spin 1/2 localized at the Sc₂ dimer and two equivalent ⁴⁵Sc nuclear spins 7/2, which yields 64 well resolved EPR transitions. We report a comprehensive analysis of the temperature dependence of the EPR spectrum of Sc₂@C₈₀(CH₂Ph) dissolved in d-toluene measured in a wide temperature range above and below the melting point. The nature of the electron spin coherence phase memory is investigated. The properties of all resonance lines in a liquid phase were treated within the model of the free rotational diffusion. Both, analytical expressions and numerical examination provide an excellent agreement between the experimental and simulated spectra. A detailed study of the experimental data confirms the assumption of the independent motions of the fullerene cage and the Sc₂ core. The data obtained show three regimes of molecular motion detected at different temperatures: the free rotation of both the fullerene cage and its bi-metal core, the motion of the core in the frozen fullerene cage, and, finally, a state with a fixed structure of both parts of the metallofullerene molecules. The data analysis reveals a significant nuclear quadrupole interaction playing an important role for the mixing of the different nuclear spin multiplets.