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Title: Mononuclear Lanthanide Complexes: Energy-Barrier Enhancement by Ligand Substitution in Field-Induced DyIII SIMs
Authors: Biswas, S
Bejoymohandas, K S
Das, S
Kalita, P
Reddy, M L P
Oyarzabal, I
Colacio, E
Chandrasekhar, V
Issue Date: 29-Jun-2017
Publisher: American Chemical Society
Citation: Inorganic Chemistry,56(14):7985–7997
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. Singlecrystal 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.
Appears in Collections:2017

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