Magneto-thermal properties and slow magnetic relaxation in Mn(II)Ln(III) complexes: Influence of magnetic coupling on the magneto-caloric effect

Abstract

A family of Mn(II)Ln(III) dinuclear and tetranuclear complexes (Ln = Gd and Dy) has been prepared from the compartmental ligands N,N’-dimethyl-N,N’-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylenediamine (H2L1 ) and N,N’,N’’-trimethyl-N,N’’-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine (H2L2 ). The Mn(II)Gd(III) complexes exhibit antiferromagnetic interactions between Mn(II) and Gd(III) ions in most cases, which are supported by Density Functional Theory (DFT) calculations. Experimental magnetostructural correlations carried out for the reported complexes and other related complexes found in bibliography show that the highest ferromagnetic coupling constants are observed in di-μ-phenoxido bridged complexes, which is due to the planarity of the Mn–(μ-O)2–Gd bridging fragment and to the high Mn– O–Gd angles. The effect of these angles has been studied by DFT calculations performed on a di-μ-phenoxido doubly bridged model. The magneto-thermal properties of the Mn(II)Gd(III) based complexes have also been measured, concluding that the magnitude of the Magneto-Caloric Effect (MCE) is due to the strength rather than to the nature of the magnetic coupling. Moreover, when two Mn(II)Gd(III) dinuclear units are connected by two carbonato-bridging ligands the MCE is enhanced, obtaining a maximum magnetic entropy change of 36.4 Jkg−1 K−1 at ΔB = 7 T and T = 2.2 K. On the other hand, one of the dinuclear Mn(II)Dy(III) complexes displays Single-Molecule Magnet (SMM) behaviour with an energy barrier of 14.8 K under an applied external field of 1000 Oe.