Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes...

A series of minimally sized regular dodecahedron-embedded metallofullerene REC₂₀ clusters (RE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) as basic units of nanoassembled materials with tunable magnetism and UV sensitivity have been explored using density functional theory (DFT). The contribution of the 4f orbital of the rare earth atom at the center of the C₂₀ cage to the frontier molecular orbital of REC₂₀ gives the REC₂₀ cluster additional stability. The AdNDP orbitals of the four REC₂₀ superatoms that conform to the spherical jellium model indicate that through natural population analysis and spin density diagrams, we observe a monotonic increase in the magnetic moment from Ce to Gd. This is attributed to the increased number of unpaired electrons in the 4f orbitals of lanthanide rare earth atoms. The UV-visible spectrum of REC20 clusters shows strong absorption in the mid-UV and near-UV bands. REC₂₀ clusters encapsulating lanthanide rare earth atoms stand out for their tunable magnetism, UV sensitivity, and stability, making them potential new self-assembly materials.