Jochim Aleksej, Lohmiller Thomas, Rams Michał, Böhme Michael, Ceglarska Magdalena, Schnegg Alexander, Plass Winfried, Näther Christian
Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, 24118 Kiel, Germany.
EPR4Energy Joint Lab, Department Spins in Energy Conversion and Quantum Information Science, Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Kekuléstrasse 5, 12489 Berlin, Germany.
Inorg Chem. 2020 Jul 6;59(13):8971-8982. doi: 10.1021/acs.inorgchem.0c00815. Epub 2020 Jun 18.
Reaction of Co(NCS) with different coligands leads to the formation of three compounds with the general composition [Co(NCS)(L)] (L = aniline (), morpholine (), and ethylenethiourea ()). In all of these compounds the cobalt(II) cations are octahedrally coordinated by two thiocyanate N and S atoms and the apical donor atoms of the coligands and are linked into linear chains by pairs of anionic ligands. The magnetic behavior was investigated by a combination of static and dynamic susceptibility as well as specific-heat measurements, computational studies, and THz-EPR spectroscopy. All compounds show antiferromagnetic ordering as observed for similar compounds with pyridine derivatives as coligands. In contrast to the latter, for - significantly higher critical temperatures and no magnetic single-chain relaxations are observed, which can be traced back to stronger interchain interactions and a drastic change in the magnetic anisotropy of the metal centers. These results are discussed and compared with those of the pyridine-based compounds, which provides important insights into the parameters that govern the magnetic behavior of such one-dimensional coordination polymers.
Co(NCS) 与不同的共配体反应生成三种通式为 [Co(NCS)(L)] 的化合物（L = 苯胺（）、吗啉（）和乙撑硫脲（））。在所有这些化合物中，钴 (II) 阳离子由两个硫氰酸根的 N 和 S 原子以及共配体的顶端供体原子八面体配位，并通过成对的阴离子配体连接成线性链。通过静态和动态磁化率以及比热测量、计算研究和太赫兹电子顺磁共振光谱相结合的方法研究了其磁行为。所有化合物都表现出反铁磁有序，这与以吡啶衍生物作为共配体的类似化合物的情况相同。与后者不同的是，对于 - 观察到显著更高的临界温度且未观察到磁单链弛豫，这可归因于更强的链间相互作用以及金属中心磁各向异性的急剧变化。对这些结果进行了讨论并与基于吡啶的化合物的结果进行了比较，这为控制此类一维配位聚合物磁行为的参数提供了重要见解。
