Journal of the American Chemical Society, Vol.138, No.6, 1916-1921, 2016
Ni9Te6(PEt3)(8)C-60 Is a Superatomic Superalkali Superparamagnetic Cluster Assembled Material (S-3-CAM)
First-principles theoretical studies enable an electronic and magnetic characterization of the recently synthesized Ni9Te6(PEt3)(8)C-60 ionic material consisting of Ni9Te6(PEt3)(8) superatoms and C-60. The PEt3 ligands are shown to create an internal coulomb well that lifts the quantum states of the Ni9Te6 cluster, lowering its ionization potential to 3.39 eV thus creating a superalkali motif. The metallic core has a spin magnetic moment of 5.3 mu(B) in agreement with experiment. The clusters are marked by low magnetic anisotropy energy (MAE) of 2.72 meV and a larger intra-exchange coupling exceeding 0.2 eV, indicating that the observed paramagnetic behavior around 10K is due to super-paramagnetic relaxations. The magnetic motifs separated by C-60 experience a weak superexchange that stabilizes a ferromagnetic ground state as observed around 2 K. The calculated MAE is sensitive to the charged state that could account for the observed change in magnetic transition temperature with size of the ligands or anion.