Synthesis, magnetic, thermal and structural properties of Co(II), Ni(II) and Cu(II) complexes containing isophthalato ligands
Rogan, Jelena ...
A series of novel ternary Co(II), Ni(II) and Cu(II) complexes containing 2,2'-dipyridylamine (dipya), 2,2'-bipyridine (bipy), and 1,10-phenanthroline (phen), as aromatic diamine ligands, and dianion ...of isophthalic acid (ipht) have been prepared by ligand exchange reactions from diluted H▫$_2$▫O/EtOH solutions. The complexes were characterized by elemental analysis, IR spectroscopy, magnetic susceptibility measurements and TG and DSC analysis. Three complexes, Cu(dipya)(ipht)▫$\cdot$▫H▫$_2$▫O (1), Co(dipya)(ipht)▫$\cdot$▫2H▫$_2$▫O (2) and Cu(ipht)(phen)▫$\cdot$▫2H▫$_2$▫O (5) are polymeric with bis-monodentate ipht, while the other two complexes M(bipy)(ipht)▫$\cdot$▫4H▫$_2$▫O, M=Co(II) (3) and Ni(II) (4), contain ipht as a counter ion. All Co(II) and Ni(II) complexes are (pseudo)octahedral, while Cu(II) complexes have square-pyramidal or distorted octahedral geometry. The variable temperature magnetic susceptibility measurements showed very weak antiferromagnetic behaviour for all complexes. Dehydration processes, decomposition mechanisms and thermal stability of 1-5 are assumed. One complex from the above series, [Ni(bipy)(H▫$_2$▫O)▫$_4$▫](ipht) (4), and one additional complex, [Co(bipy)(ipht)]▫$_n$▫ (6), are obtained as single-crystals and their structures are determined from X-ray diffraction data. In both structures M(II) centers are in deformed octahedral environment and they are linked by hemi-ipht ligands (4) and two different bridging ipht ligands (6). Three-dimensional networks in 4 and 6 are governed by strong noncovalent interactions. The cations and ipht anions in 4 are connected by hydrogen bonds building double layers parallel to ▫$ab$▫-plane that are further packed by ▫$\pi-\pi$▫ interactions. In 6 double chains extending along ▫$b$▫-axis are strengthened by interchain ▫$\pi-\pi$▫ interactions constructing a three-dimensional framework.
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