Fine-tuning terminal solvent ligands to rationally enhance the energy barrier in dinuclear dysprosium single-molecule magnets

In search of simple approaches to rationally enhance the energy barriers in polynuclear dysprosium single-molecule magnets, a new system containing two structurally closely related dinuclear dysprosium complexes, namely [Dy2(L)2(DBM)2(DMF)2] (1) and [Dy2(L)2(DBM)2(DMA)2]·2DMA (2) (HDBM = dibenzoylmethane, H2L = 2-hydroxy-N'-(2-hydroxy-3-methoxybenzylidene)benzohydrazide), is introduced and the structure-dependent magnetic properties are investigated. The two complexes display only slight variations in the coordination geometries of the Dy(iii) ion but display remarkably different magnetic behaviors. By replacing the DMF (dimethylformamide) ligand in complex 1 with DMA (dimethylacetamide) in 2 while retaining the same coordination atoms, we were able to create a 3-fold enhancement in the energy barrier, from 24 K for complex 1 to 77 K for complex 2. Complete-active-space self-consistent field (CASSCF) calculations revealed that the charge distribution surrounding the Dy(iii) centers in 1 and 2 is the key factor in determining the relaxation properties of the SMMs. The introduction of an electron-donating CH3 group in DMA to replace the hydrogen in DMF resulted in a larger average charge along the magnetic axes of complex 2 compared to complex 1, which resulted in a stronger easy-axis ligand field, thus increasing the energy difference between the ground and the first excited states of complex 2. This work presents a simple method to rationally enhance the energy barrier in polynuclear lanthanide SMMs through fine-tuning of the electrostatic potential of the atoms along the magnetic axis.