Syntheses, structures and magnetisms of dimethyl phosphate-bridged dinuclear lanthanide complexes with pentadentate macrocyclic ligand

Abstract

A series of air-stable dinuclear complexes, [HNEt3]2[Ln2(L)2((CH3O)2PO2)4](BPh4)4 (L = 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca1(19), 2,13,15,17-pentene, Ln = Dy, 1-Dy; Tb, 2-Tb; Gd, 3-Gd), has been synthesized and characterized using single-crystal X-ray crystallography and magnetic measurements. The crystal structures disclose that two dimethyl phosphate anions act as bridging ligands, linking two Ln(III) ions. Each Ln(III) ion is eight-coordinated by five nitrogen atoms from a pentadentate Schiff based ligand L and three oxygen atoms from three dimethyl phosphates, forming a triangular dodecahedral coordination geometry. Direct-current magnetic susceptibility measurements indicate an extremely weak antiferromagnetic exchange between Gd(III) ions in 3-Gd. Complex 1-Dy exhibits slow magnetic relaxation with an effective energy barrier (Ueff) of 13 K under an applied field of 1000 Oe, whereas 2-Tb does not exhibit single-molecule magnet behavior. This work presents a novel strategy for constructing polynuclear single-molecular magnets by using a pentadetate macrocycle as magnetic building blocks integrated with replaceable axial ligands.