Breaking Symmetry Relaxes Structural and Magnetic Restraints, Suppressing QTM in Enantiopure Butterfly Fe(2)Dy(2) SMMs

The {Fe(2)Dy(2)} butterfly systems can show single molecule magnet (SMM) behaviour, the nature of which depends on details of the electronic structure, as previously demonstrated for the [Fe(2)Dy(2)(μ(3)‐OH)(2)(Me‐teaH)(2)(O(2)CPh)(6)] compound, where the [N,N‐bis‐(2‐hydroxyethyl)‐amino]‐2‐propanol (Me‐teaH(3)) ligand is usually used in its racemic form. Here, we describe the consequences for the SMM properties by using enantiopure versions of this ligand and present the first homochiral 3d/4 f SMM, which could only be obtained for the S enantiomer of the ligand for [Fe(2)Dy(2)(μ(3)‐OH)(2)(Me‐teaH)(2)(O(2)CPh)(6)] since the R enantiomer underwent significant racemisation. To investigate this further, we prepared the [Fe(2)Dy(2)(μ(3)‐OH)(2)(Me‐teaH)(2)(O(2)CPh)(4)(NO(3))(2)] version, which could be obtained as the RS‐, R‐ and S‐compounds. Remarkably, the enantiopure versions show enhanced slow relaxation of magnetisation. The use of the enantiomerically pure ligand suppresses QTM, leading to the conclusion that use of enantiopure ligands is a “gamechanger” by breaking the cluster symmetry and altering the intimate details of the coordination cluster's molecular structure.