Strictly linear trinuclear Dy-Ca/Mg-Dy single-molecule magnets: the impact of long-range f-f ferromagnetic interactions on suppressing quantum tunnelling of magnetization leading to slow magnetic relaxation.

Abstract

The synthesis, structural characterization and magnetic properties of four heterometallic complexes with formulas Ln2M(OQ)8 [Ln(iii) = Dy, M(ii) = Ca (1), Mg (2); Ln(iii) = Er, M(ii) = Ca (3), Mg (4); HOQ = 8-hydroxyquinoline] are reported. Complexes display a perfectly linear arrangement of three metal ions involving two terminal Ln(iii) ions and one central alkaline earth M(ii) ion, and they are bridged by three phenolato oxygen atoms from three 8-hydroxyquinoline ligands. Direct-current (dc) magnetic susceptibility studies show that there exists a long-range ferromagnetic (FM) interaction between two f-electronic centers in Dy-based complexes 1 and 2 albeit they are separated by diamagnetic alkaline earth ions, and the FM interaction has been successfully reproduced by ab initio calculations. Alternating current (ac) magnetic susceptibility measurements indicate that complexes 1 and 2 exhibit significant single-molecule magnet (SMM) behaviors. This is mostly attributed to the parallel magnetic axes of individual Dy(iii) sites aligning closely to the Dy-M-Dy direction, and the linearly extending magnetic susceptibility tensors of each ion lead to the FM interaction. The dc and ac susceptibility studies of the intramolecularly diluted complexes reveal that the f-f coupling suppresses the QTMs significantly in the absence of the external magnetic field.