Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet

Höke V, Gieb K, Mueller P, Ungur L, Chibotaru LF, Heidemeier M, Krickemeyer E, Stammler A, Bögge H, Schroeder C, Schnack J, et al. (2012)
Chemical Science 3(9): 2868-2882.

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Abstract
We have synthesized the triplesalen-based single-molecule magnet (SMM) [Mn-III Mn-6(III)](3+) as a variation of our SMM [Mn-III Cr-6(III)](BPh4)(3). The use of the rod-shaped anion lactate (lac) was intended to enforce a rod packing and resulted in the crystallization of [ MnIII 6MnIII](lac) 3 in the highly symmetric space group R3. This entails a crystallographic S-6 symmetry of the [Mn-III Mn-6(III)](3+) molecules, which in addition are all aligned with the crystallographic c axis. Moreover, the molecular environment of each [Mn-III Mn-6(III)](3+) molecule is highly symmetric. Single-crystals of [Mn-III Mn-6(III)](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 approximate to 3.4 T with a hysteretic opening up to 10 T. Ab initio calculations including spin-orbit coupling establish a nonmagnetic 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 [Mn-III Mn-6(III)](3+) is in the limit of weak exchange (J << D) with antiferromagnetic interactions in the trinuclear Mn-3(III) triplesalen subunits resulting in intermediate S* = 2 spins. Slight ferromagnetic interactions between the two trinuclear Mn-3(III) 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 approximate to 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 [Mn-III Mn-6(III)](3+) single-molecule magnet with hysteretic openings up to 10 T.
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Höke V, Gieb K, Mueller P, et al. Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. Chemical Science. 2012;3(9):2868-2882.
Höke, V., Gieb, K., Mueller, P., Ungur, L., Chibotaru, L. F., Heidemeier, M., Krickemeyer, E., et al. (2012). Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. Chemical Science, 3(9), 2868-2882.
Höke, V., Gieb, K., Mueller, P., Ungur, L., Chibotaru, L. F., Heidemeier, M., Krickemeyer, E., Stammler, A., Bögge, H., Schroeder, C., et al. (2012). Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. Chemical Science 3, 2868-2882.
Höke, V., et al., 2012. Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. Chemical Science, 3(9), p 2868-2882.
V. Höke, et al., “Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet”, Chemical Science, vol. 3, 2012, pp. 2868-2882.
Höke, V., Gieb, K., Mueller, P., Ungur, L., Chibotaru, L.F., Heidemeier, M., Krickemeyer, E., Stammler, A., Bögge, H., Schroeder, C., Schnack, J., Glaser, T.: Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet. Chemical Science. 3, 2868-2882 (2012).
Höke, Veronika, Gieb, Klaus, Mueller, Paul, Ungur, Liviu, Chibotaru, Liviu F., Heidemeier, Maik, Krickemeyer, Erich, Stammler, Anja, Bögge, Hartmut, Schroeder, Christian, Schnack, Jürgen, and Glaser, Thorsten. “Hysteresis in the ground and excited spin state up to 10 T of a [(Mn6MnIII)-Mn-III](3+) triplesalen single-molecule magnet”. Chemical Science 3.9 (2012): 2868-2882.
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