✍ Scribed by Valeriu Mereacre; Ayuk M. Ako; Rodolphe Clérac; Wolfgang Wernsdorfer; Ian J. Hewitt; Christopher E. Anson; Annie K. Powell
No coin nor oath required. For personal study only.
The reaction of [Mn~6~O~2~(Piv)~10~(4‐Me‐py)~2.5~(PivH)~1.5~] (1) (py: pyridine, Piv: pivilate) with N‐methyldiethanolamine (mdeaH~2~) and Ln(NO~3~)~3~⋅6 H~2~O in MeCN leads to a series of nonanuclear compounds [Mn~5~Ln~4~(O)~6~(mdea)~2~(mdeaH)~2~(Piv)~6~(NO~3~)~4~(H~2~O)~2~]⋅2 MeCN (Ln=Tb^III^ (2), Dy^III^ (3), Ho^III^ (4), Y^III^ (5)). Single‐crystal X‐ray diffraction shows that compounds 2–5 are isostructural, with the central core composed of two distorted {Mn^IV^Mn^III^Ln~2~O~4~} cubanes sharing a Mn^IV^ vertex, representing a new heterometallic 3d–4f motif for this class of ligand. The four new compounds display single‐molecule magnet (SMM) behaviour, which is modulated by the lanthanide ion used. Moreover, the values found for Δ~eff~ and τ~o~ for 3 of 38.6 K and 3.0×10^−9^ s respectively reveal that the complex 3 exhibits the highest energy barrier recorded so far for 3d–4f SMMs. The slow relaxation of the magnetisation for 3 was confirmed by μ‐SQUID measurements on an oriented single crystal and the observation of M versus H hysteresis loops below 1.9 K.
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