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Mixed-valence dilanthanide complexes of the type (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln–Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (CpiPr5)2Ln2I3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln–Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin–spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide–lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm–1. Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo5 and Nd2Fe14B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers.
Kwon et al. (Wed,) studied this question.