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Interplay of Spin Crossover and Coordination-Induced Spin State Switch for Iron Bis(pyrazolyl)methanes in Solution
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-10-01 , DOI: 10.1021/acs.inorgchem.0c02306
Kristina Keisers 1 , Henrika M. Hüppe 1 , Linda Iffland-Mühlhaus 2 , Alexander Hoffmann 1 , Christoph Göbel 3 , Ulf-Peter Apfel 2, 4 , Birgit Weber 3 , Sonja Herres-Pawlis 1
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-10-01 , DOI: 10.1021/acs.inorgchem.0c02306
Kristina Keisers 1 , Henrika M. Hüppe 1 , Linda Iffland-Mühlhaus 2 , Alexander Hoffmann 1 , Christoph Göbel 3 , Ulf-Peter Apfel 2, 4 , Birgit Weber 3 , Sonja Herres-Pawlis 1
Affiliation
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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.
中文翻译：
溶液中铁双（吡唑基）甲烷的自旋交叉和配位诱导的自旋状态转换的相互作用
双（吡唑基）双吡啶基甲烷铁（II）配合物在不同溶剂中表现出通用的自旋态转换行为。在固体中，化合物的磁性能已通过X射线衍射，Mößbauer光谱和SQUID磁力分析进行了表征，并指向高自旋态。对于腈类溶剂，配合物的溶剂化会导致配位环境从{N 5 O}变为{N 6并导致温度依赖的SCO行为。这种转变的热力学性质是通过紫外/可见光谱，SQUID测量和Evans NMR方法获得的。此外，通过使用甲醇作为溶剂，观察到配位诱导的自旋状态转换（CISSS）转变为低自旋，这是由配位球的重排触发的。通过改变MeCN中配体与金属的化学计量比，可以观察到相同的行为，该过程是可逆的。这种转变通过紫外/可见光谱法进行监测，然后通过X射线衍射，穆斯堡尔光谱法和SQUID测量以固态表征首次形成的双（吡唑基）甲烷新的双子午线配位基序。这些可转换特性依赖于不同类型的溶剂的复杂关联表明，不应低估溶剂对配位环境和磁性的影响。此外，需要仔细研究以区分热诱导的自旋交叉和配位诱导的自旋状态转换。
更新日期：2020-10-21
中文翻译：
溶液中铁双（吡唑基）甲烷的自旋交叉和配位诱导的自旋状态转换的相互作用
双（吡唑基）双吡啶基甲烷铁（II）配合物在不同溶剂中表现出通用的自旋态转换行为。在固体中，化合物的磁性能已通过X射线衍射，Mößbauer光谱和SQUID磁力分析进行了表征，并指向高自旋态。对于腈类溶剂，配合物的溶剂化会导致配位环境从{N 5 O}变为{N 6并导致温度依赖的SCO行为。这种转变的热力学性质是通过紫外/可见光谱，SQUID测量和Evans NMR方法获得的。此外，通过使用甲醇作为溶剂，观察到配位诱导的自旋状态转换（CISSS）转变为低自旋，这是由配位球的重排触发的。通过改变MeCN中配体与金属的化学计量比，可以观察到相同的行为，该过程是可逆的。这种转变通过紫外/可见光谱法进行监测，然后通过X射线衍射，穆斯堡尔光谱法和SQUID测量以固态表征首次形成的双（吡唑基）甲烷新的双子午线配位基序。这些可转换特性依赖于不同类型的溶剂的复杂关联表明，不应低估溶剂对配位环境和磁性的影响。此外，需要仔细研究以区分热诱导的自旋交叉和配位诱导的自旋状态转换。
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