Modeling Spin Interactions in a Triangular Cobalt(II) Complex with Triaminoguanidine Ligand Framework: Synthesis, Structure, and Magnetic Properties
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PLAUL, Daniel, BOHME, Michael, OSTROVSKY, Sergei M., TOMKOWICZ, Zbigniew, GORLS, Helmar, HAASE, Wolfgang, PLASS, Winfried. Modeling Spin Interactions in a Triangular Cobalt(II) Complex with Triaminoguanidine Ligand Framework: Synthesis, Structure, and Magnetic Properties. In: Inorganic Chemistry, 2018, vol. 57, pp. 106-119. ISSN 0020-1669. DOI: https://doi.org/10.1021/acs.inorgchem.7b02229
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Inorganic Chemistry
Volumul 57 / 2018 / ISSN 0020-1669

Modeling Spin Interactions in a Triangular Cobalt(II) Complex with Triaminoguanidine Ligand Framework: Synthesis, Structure, and Magnetic Properties

DOI:https://doi.org/10.1021/acs.inorgchem.7b02229

Pag. 106-119

Plaul Daniel1, Bohme Michael1, Ostrovsky Sergei M.2, Tomkowicz Zbigniew3, Gorls Helmar1, Haase Wolfgang4, Plass Winfried1
 
1 Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Humboldtstr,
2 Institute of Applied Physics, Academy of Sciences of Moldova,
3 Jagiellonian University in Krakow,
4 Technical University Darmstadt
 
 
Disponibil în IBN: 23 februarie 2018


Rezumat

The new tritopic triaminoguanidine-based ligand 1,2,3-tris[(pyridine-2-ylmethylidene)amino]guanidine (H2pytag) was synthesized. The reaction of a mixture of cobalt(II) chloride and cobalt(II) perchlorate with the ligand H2pytag in pyridine solution leads to the formation of the trinuclear cobalt(II) complex [Co3(pytag)(py)6Cl3]ClO4. Three octahedrally coordinated high-spin cobalt(II) ions are linked through the bridging triaminoguanidine backbone of the ligand leading to an almost equilateral triangular arrangement. The magnetic properties of the complex were investigated by magnetic measurements, variable-temperature, variable-field magnetic circular dichroism (MCD) spectroscopy, and density functional theory as well as ab initio calculations. A rather strong antiferromagnetic exchange interaction between the cobalt(II) centers of ca. -12 cm-1 is determined together with a strong local anisotropy. The single-ion anisotropy of all three cobalt(II) centers is found to be easy-plane, which coincides with the tritopic ligand plane. MCD measurements and theoretical investigations demonstrate the presence of rhombic distortion of the local Co surrounding.