Interplay of Spin Crossover and Coordination-Induced Spin State Switch for Iron Bis(pyrazolyl)methanes in Solution

Titelangaben

Keisers, Kristina ; Hüppe, Henrika ; Iffland-Mühlhaus, Linda ; Hoffmann, Alexander ; Göbel, Christoph ; Apfel, Ulf-Peter ; Weber, Birgit ; Herres-Pawlis, Sonja:
Interplay of Spin Crossover and Coordination-Induced Spin State Switch for Iron Bis(pyrazolyl)methanes in Solution.
In: Inorganic Chemistry. Bd. 59 (2020) Heft 20 . - S. 15343-15354.
ISSN 1520-510X
DOI: https://doi.org/10.1021/acs.inorgchem.0c02306

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Abstract

Bis(pyrazolyl)bipyridinylmethane iron(II) complexes show a versatile spin state switching behavior in different solvents. In the solid, the magnetic properties of the compounds have been characterized by X-ray diffraction, Mößbauer spectroscopy, and SQUID magnetometry and point toward a high spin state. For nitrilic solvents, the solvation of the complexes leads to a change of the coordination environment from {N5O} to {N6} and results in a temperature-dependent SCO behavior. Thermodynamic properties of this transformation are obtained via UV/vis spectroscopy, SQUID measurements, and the Evans NMR method. Moreover, a coordination-induced spin state switch (CISSS) to low spin is observed by using methanol as solvent, triggered through a rearrangement of the coordination sphere. The same behavior can be observed by changing the stoichiometry of the ligand-to-metal ratio in MeCN, where the process is reversible. This transformation is monitored via UV/vis spectroscopy, and the resulting new bis-meridional coordination motif, first described for bis(pyrazolyl)methanes, is characterized in the solid state via X-ray diffraction, Mößbauer spectroscopy, and SQUID measurements. The sophisticated correlation of these switchable properties in dependence on different types of solvents reveals that the influence of the solvent on the coordination environment and magnetic properties should not be underestimated. Furthermore, careful investigation is necessary to differentiate between a thermally-induced spin crossover and a coordination-induced spin state switch.