A family of 3d metal clusters based on N–N single bonds bridged quasi-linear trinuclear cores: the Mn analogue displaying single-molecule magnet behavior

Abstract

The reactions of the diacylhydrazine ligands N,N′-bisalicyl-2,6-pyridine dicarbohydrazide (H₆sphz) and N,N′-bis(3-methoxysalicyl)-2,6-pyridine dicarbohydrazide (H₆msphz) with various 3d metal salts, afforded a series of coordination clusters, namely, [Mn^III₂Mn^II(sphz)(acac)₂(CH₃OH)₄] (1, acac⁻ = acetylacetone anions), [Ni^II₃(msphz)(Py)₄] (2, Py = pyridine), [Cu^II₆(sphz)₂(Py)₄] (3) and [Cu^II₆(msphz)₂(Py)₄]·2DMF·2H₂O (4). Cluster 1 and 2 are single ligand assembled quasi-linear trinuclear structures. Both 3 and 4 consist a pair of quasi-linear {Cu₃} cores, which are linked together by two crossed ligands. The adjacent 3d metal ions in all trinuclear cores of 1–4 are bridged by N–N single bonds of ligands, which convey ferromagnetic (FM) interactions between 3d metal centers of 1, and antiferromagnetic (AFM) interactions between those of 2–4. In particular, the FM interactions and linear arrangement of mixed-valence Mn centers in 1 result in a large spin ground states value (S_T) of 13/2, as well as single-molecule magnet (SMM) behavior of slow relaxation and hysteresis of magnetization.