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Issue 9, 2012
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Hysteresis in the ground and excited spin state up to 10 T of a [MnIII6MnIII]3+ triplesalen single-molecule magnet

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We have synthesized the triplesalen-based single-molecule magnet (SMM) [MnIII6MnIII]3+ as a variation of our SMM [MnIII6CrIII](BPh4)3. The use of the rod-shaped anion lactate (lac) was intended to enforce a rod packing and resulted in the crystallization of [MnIII6MnIII](lac)3 in the highly symmetric space group R[3 with combining macron]. This entails a crystallographic S6 symmetry of the [MnIII6MnIII]3+ molecules, which in addition are all aligned with the crystallographic c axis. Moreover, the molecular environment of each [MnIII6MnIII]3+ molecule is highly symmetric. Single-crystals of [MnIII6MnIII](lac)3 exhibit a double hysteresis at 0.3 K with a hysteretic opening not only for the spin ground state up to 1.8 T, but also for an excited state becoming the ground state at ≈ 3.4 T with a hysteretic opening up to 10 T. Ab initio calculations including spin-orbit coupling establish a non-magnetic behavior of the central MnIII low-spin (l.s.) ion at low temperatures, demonstrating that predictions from ligand-field theory are corroborated in the case of MnIII l.s. by ab intio calculations. Simulations of the field- and temperature-dependent magnetization data indicate that [MnIII6MnIII]3+ is in the limit of weak exchange (JD) with antiferromagnetic interactions in the trinuclear MnIII3 triplesalen subunits resulting in intermediate S* = 2 spins. Slight ferromagnetic interactions between the two trinuclear MnIII3 subunits lead to a ground state in zero-field that is approximately described by a total spin quantum number S = 4. This ground state exhibits only a very small anisotropy barrier due to the misalignment of the local zero-field splitting tensors. At higher magnetic fields of ≈ 3.4 T, the spin configuration changes to an all-up orientation of the local MnIII spins, with the main part of the Zeeman energy needed for the spin-flip being required to overcome the local MnIII anisotropy barriers, while only minor contributions of the Zeeman energy are needed to overcome the antiferromagnetic interactions. These combined theoretical analyses provide a clear picture of the double-hysteretic behavior of the [MnIII6MnIII]3+ single-molecule magnet with hysteretic openings up to 10 T.

Graphical abstract: Hysteresis in the ground and excited spin state up to 10 T of a [MnIII6MnIII]3+ triplesalen single-molecule magnet

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The article was received on 22 May 2012, accepted on 18 Jun 2012 and first published on 19 Jun 2012

Article type: Edge Article
DOI: 10.1039/C2SC20649H
Citation: Chem. Sci., 2012,3, 2868-2882
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    Hysteresis in the ground and excited spin state up to 10 T of a [MnIII6MnIII]3+ triplesalen single-molecule magnet

    V. Hoeke, K. Gieb, P. Müller, L. Ungur, L. F. Chibotaru, M. Heidemeier, E. Krickemeyer, A. Stammler, H. Bögge, C. Schröder, J. Schnack and T. Glaser, Chem. Sci., 2012, 3, 2868
    DOI: 10.1039/C2SC20649H

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