SMM Behavior Tuned by an Exchange Coupling LEGO Approach for Chimeric Compounds: First 2p-3d-4f Heterotrispin Complexes with Different Metal Ions Bridged by One Aminoxyl Group.

ABSTRACT

Coordination compounds containing three different spin carriers (2p, 3d, and 4f), with the general formula [MIIDyIII(LH)(hfac)5] (M = Co, Ni, Mn, Zn), have been obtained using Mannich ligands decorated with a nitronyl-nitroxide fragment. The synthetic approach is general and leads to binuclear 3d-4f complexes, the two metal ions being bridged by one aminoxyl group and by one oxygen atom arising from a hfac- ligand. Triangular spin topology affords significant 2p-3d, 3d-4f, and 2p-4f exchange interactions. For the [CoIIDyIIIRad] derivative obtained using a nitronyl-nitroxide chiral ligand, a high energy barrier (∼200 cm-1) and a slow relaxation behavior below 30 K were found and rationalized by ab initio calculations. The improvement of magnetic properties comes from the synergy of optimal single ions properties and exchange couplings contributions where the CoII-Rad interaction becomes the leading one. The role played by this interaction is clearly proved by the investigation of the magnetic properties of the [ZnIIDyIIIRad] derivative, with a much lower energy barrier (12.7 cm-1) and by the lack of SMM behavior of the previously reported [CoIIDyIIIRad] compound ( Chem. Commun . 2017 , 53 , 6504 ), with a linear topology of spin carriers and a negligible CoII-Rad interaction.