Tailoring magnetic properties in Mn4 molecules: A way to develop single-molecule magnets
Distorted cubane Mn4+Mn3+ 3 single-molecule magnets (SMMs) having the general chemical formula Mn4+Mn 3+ 3(3-L2-)3( 3-X-)(OAc)- 3(dbm)- 3 (L O; X various; dbmH dibenzoyl-methane), have been studied using first-principles calculations. It was shown in our previous paper that the ferrimagnetic structure of Mn4+Mn3+ 3 SMMs is dominated by the type hybridization between the dz2 orbitals at the three high-spin Mn3+ ions and the t2g orbitals at the Mn4+ ion. This result allows us to predict that the ferrimagnetic structure of Mn4+Mn3+ 3 molecules will be the most stable with the Mn4+-(3-L2-)-Mn 3+ angle ≈ 90, while synthesized Mn4+Mn 3+ 3 molecules have ≈ 95. To design new Mn 4+Mn3+ 3 molecules having a much more stable ferrimagnetic state, one following approach is suggested: Controlling the Mn4+-(3-L2-)-Mn3+ exchange pathways by rational variations in ligands to strengthen the hybridization between Mn ions. By employed N-based ligands to form the Mn4+-(μ3- L2-)-Mn3+ exchang...