Influence of the Coligand onto the Magnetic Anisotropy and the Magnetic Behavior of One-Dimensional Coordination Polymers.

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.