Synthesis, structures and magnetic studies of hexanuclear lanthanide complexes: SMM behavior of the DyIII analogue and MCE properties of the GdIII analogue

The synthesis, structure and magnetic properties of homometallic hexanuclear lanthanide complexes [Ln6(HL)4(tfa)4(S)2]·2NO3·x H2O·yMeOH (1, Ln = Gd, S = MeOH, x = 0, y = 0; 2, Ln = Tb, S = H2O, x = 2, y = 2; 3, Ln = Dy, S = MeOH, x = 0, y = 2; 4, Ln = Er, S = MeOH, x = 0, y = 2). [(H4L) = 6-((bis(2-hydroxyethyl)amino)-N'-(2-hydroxybenzylidene)picolinohydrazide) (tfa = trifloroacetylacetone)] are reported. These hexanuclear assemblies are made up of two trinuclear triangular sub-units linked through the oxygen atoms of two phenoxide bridging groups in a corner sharing arrangement. Magnetic studies reveal that 1 displays a magnetocaloric effect with a maximum value of -ΔSm = 21.03 J kg-1 K-1 at T = 3 K and under an applied field change ΔB = 5 T. Complex 3 shows slow relaxation of magnetization even under zero applied field although a clear maximum in the ac susceptibility plots cannot be seen. However, under an optimal applied field of 0.2 T, clear maxima are observed in the out-of-phase (χ''M) component of the ac susceptibility in the temperature range 3.5 K (2 kHz) to 10.5 K (10 kHz). The temperature dependence of the relaxation times could be fitted to the sum of Orbach, Raman and QTM relaxation processes affording the following parameters: τo = 3.4(9) × 10-8 s, Ueff = 94(2) K, BRaman = 16.43(1) K-n s-1, n = 3.2(3) and τQTM = 0.0044(3) s. 4, under an applied magnetic field of 0.2 T, shows slow relaxation of magnetization through a thermally activated Orbach process with Ueff = 18.2(9) K and τo = 3.5(3) × 10-8 s.