Trends in trigonal prismatic Ln-[1]ferrocenophane complexes and discovery of a Ho3+ single-molecule magnet. Academic Article uri icon

abstract

  • Lanthanide metallocenophanes are an intriguing class of organometallic complexes that feature rare six-coordinate trigonal prismatic coordination environments of 4f elements with close intramolecular proximity to transition metal ions. Herein, we present a systematic study of the structural and magnetic properties of the ferrocenophanes, [LnFc3(THF)2Li2]-, of the late trivalent lanthanide ions (Ln = Gd (1), Ho (2), Er (3), Tm (4), Yb (5), Lu (6)). One major structural trend within this class of complexes is the increasing diferrocenyl (Fc2-) average twist angle with decreasing ionic radius (r ion) of the central Ln ion, resulting in the largest average Fc2- twist angles for the Lu3+ compound 6. Such high sensitivity of the twist angle to changes in r ion is unique to the here presented ferrocenophane complexes and likely due to the large trigonal plane separation enforced by the ligand (>3.2 ). This geometry also allows the non-Kramers ion Ho3+ to exhibit slow magnetic relaxation in the absence of applied dc fields, rendering compound 2 a rare example of a Ho-based single-molecule magnet (SMM) with barriers to magnetization reversal (U) of 110-131 cm-1. In contrast, compounds featuring Ln ions with prolate electron density (3-5) don't show slow magnetization dynamics under the same conditions. The observed trends in magnetic properties of 2-5 are supported by state-of-the-art ab initio calculations. Finally, the magneto-structural relationship of the trigonal prismatic Ho-[1]ferrocenophane motif was further investigated by axial ligand (THF in 2) exchange to yield [HoFc3(THF*)2Li2]- (2-THF*) and [HoFc3(py)2Li2]- (2-py) motifs. We find that larger average Fc2- twist angles (in 2-THF* and 2-py as compared to in 2) result in faster magnetic relaxation times at a given temperature.

published proceedings

  • Chem Sci

author list (cited authors)

  • Latendresse, T. P., Vieru, V., Upadhyay, A., Bhuvanesh, N. S., Chibotaru, L. F., & Nippe, M.

publication date

  • January 1, 2020 11:11 AM