Mononuclear Lanthanide Complexes: Energy-Barrier Enhancement by Ligand Substitution in Field-Induced Dy^III SIMs

Abstract

The sequential reaction of 2-((6-(hydroxymethyl)pyridin-2-yl)-methyleneamino)phenol (LH₂), LnCl₃·6H₂O, and 1,1,1-trifluoroacetylacetone (Htfa) in the presence of Et₃N afforded [Ln(LH) (tfa)₂] [Ln = Dy³⁺ (1), Ln = Tb³⁺ (2), and Ln = Gd³⁺ (3)], while under the same reaction conditions, but in the absence of the coligand, another series of mononuclear complexes, namely, [Ln(LH)₂]·Cl·2MeOH] [Ln = Dy³⁺ (4) and Tb³⁺ (5)] are obtained. Single-crystal X-ray diffraction analysis revealed that the former set contains a mono-deprotonated [LH]^- and two tfa ligands, while the latter set comprises of two mono-deprotonated [LH]^- ligands that are nearly perpendicular to each other at an angle of 86.9°. Among these complexes, 2 exhibited a ligand-sensitized lanthanide-characteristic emission. Analyses of the alternating current susceptibility measurements reveal the presence of single-molecule magnet behavior for 1 and 4, in the presence of direct-current field, with effective energy barriers of 4.6 and 44.4 K, respectively. The enhancement of the effective energy barrier of the latter can be attributed to the presence of a large energy gap between the ground and first excited Kramers doublets, triggered by the change in coordination environments around the lanthanide centers.