Polyoxometalates are model systems in molecular magnetism due to their ability to host magnetic ions in chemically tailored environments of high symmetry and rigidity while maintaining their integrity in the solid state and in solution. Although ab initio calculations are relatively uncommon for polyoxometalate-based SMMs, the inclusion of electrostatic effects of a crystal lattice on a Ln 3+ ion in such calculations affords a substantially better reproduction of experimental crystal field energy levels and simulated static magnetic properties than those obtained when calculated for an isolated polyanion. A combined experimental and ab initio approach into unusual axial symmetries, may open exciting opportunities for the understanding rigid molecular spin qubits. This may contribute to existing design parameters that are enabling chemists to target specific properties in novel SMMs as well as specific quantum properties exploited in emerging quantum technologies. To facilitate this, teaching the experimental aspects of Ln-SMMs requires complimentary theoretical studies for a more complete understanding.