Octanuclear [Ni(4)(II)Ln(4)(III)] complexes. Synthesis, crystal structures and magnetocaloric properties

Two original heterooctanuclear [Ni(4)(II)Ln(4)(III)] complexes (Ln(III) = Sm-III, Gd-III) have been obtained starting from the [Ni-II(valpn)(H2O)(2)] mononuclear precursor [H(2)valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)] and the corresponding lanthanide nitrates, in the presence of azide anions, through slow capture of atmospheric CO2. Three weak and competitive exchange interactions, J(GdGd), J(GdNi), J(NiNi), make the ground state of this magnetic system degenerate at cryogenic temperature and zero field. This, along with the high spin of Gd-III, lead to a significant magnetocaloric effect spread in the temperature range 1 to 20 K (Delta S-m[0-7 T, 3.5 K] = 19 J kg(-1) K-1).