Long-Range Ferromagnetic Exchange Interactions Mediated by Mn-Ce^IV-Mn Superexchange Involving Empty 4f Orbitals

Reactions involving reductive aggregation of MnO₄^- in methanol in the presence of Ce^IV and an excess of carboxylic acid have led to the synthesis of structurally related Ce/Mn clusters, [Ce₃Mn₅O₈(OMe)(O₂CBu^t)₁₃(MeOH)] (1) and [Ce₂Mn₃O₅(O₂CPh)₉(MeOH)₃] (2), containing at least one {Mn₂Ce₂O₄} cubane unit. The cores of both clusters contain Mn units separated by three (1) or two (2) Ce^IV ions. Fits of variable-temperature, solid-state dc and ac magnetic susceptibility data reveal dominant ferromagnetic interactions within 1 and 2, resulting in the maximum S = ¹⁷/₂ and S = 5 ground state spins, respectively, and thus suggesting significant ferromagnetic (F) interactions between the Mn units that are ≥6 Å apart and separated by four intervening bonds through diamagnetic Ce^IV. Fits of magnetic susceptibility data also revealed unusual long-range F interactions, and this finding was further supported by high-field EPR measurements and simulations. Density functional theory calculations and a Wannier function analysis confirm long-range interactions and indicate a Mn-Ce-Mn superexchange pathway via Mn-d/Ce-f orbital overlap/hybridization.