The Relevance of Non-axiality and Low-lying Excited States for Slow Magnetic Relaxation in Pentagonal-bipyramidal Erbium(III) Complexes Probed by High-frequency EPR

Abstract

High-frequency/high-field electron paramagnetic resonance studies on a series of seven-coordinate pentagonal-bipyramidal (PBP) erbium(III) complexes Er(DAPMBH/H$_2$DAPS)X (H$_2$DAPMBH = 2,6-diacetylpyridine bis-4-methoxy benzoylhydrazone, H$_4$DAPS = 2,6-diacetylpyridine bis-(salicylhydrazone)) demonstrate the effects of different apical ligands (X = (H$_2$O)Cl (1), (CH$_3$OH)N$_3$ (2), Cl$_2$ (3)) on the local magnetic anisotropy of the central Er(III) ions. In particular, we report direct experimental determination of the effective $g$-values and zero field splittings of the energetically low-lying Kramers doublets. Our quantitative determination of the magnetic anisotropy highlights the relevance of an axial $g$-tensor for SMM behaviour and suggests that fast magnetic relaxation is mainly driven by a thermally assisted quantum tunnelling process via low-lying excited states.