Magnetic Anisotropy Trends along a Full 4f-Series: The Effect.

The combined experimental and computational study of the 13 magnetic complexes belonging to the Na[LnDOTA(HO)] (HDOTA = tetraazacyclododecane-,',″,‴-tetraacetic acid and Ln = Ce-Yb) family allowed us to identify a new trend: the orientation of the magnetic anisotropy tensors of derivatives differing by seven electrons practically coincide. We name this trend the effect. Experiments and theory fully agree on the match between the magnetic reference frames (e.g., the easy, intermediate, and hard direction). The shape of the magnetic anisotropy of some couples of ions differing by seven f electrons might seem instead different at first look, but our analysis explains a hidden similarity. We thus pave the way toward a reliable predictivity of the magnetic anisotropy of lanthanide complexes with a consequent reduced need of computational and synthetical efforts. We also offer a way to gain information on ions with a relatively small total angular momentum (i.e., Sm and Eu) and on the radioactive Pm, which are difficult to investigate experimentally.