Exploring the Magnetic Properties of the Largest Single-Molecule Magnets.

The giant {Mn70} and {Mn84} wheels are the largest nuclearity single-molecule magnets synthesized to date, and understanding their magnetic properties poses a challenge to theory. Starting from first-principles calculations, we explore the magnetic properties and excitations in these wheels using effective spin Hamiltonians. We find that the unusual geometry of the superexchange pathways leads to weakly coupled {Mn7} subunits carrying an effective S = 2 spin. The spectrum exhibits a hierarchy of energy scales and massive degeneracies, with the lowest-energy excitations arising from Heisenberg-ring-like excitations of the {Mn7} subunits around the wheel. We further describe how weak longer-range couplings can select the precise spin ground-state of the Mn wheels out of the nearly degenerate ground-state band.