Correlation between structure and thermal properties in 2-hydroxy-benzophenone Co(II) complexes

In this study, simultaneous TG/DTG–DTA technique was used for the simple cobalt(II) complex [Co(dpamH)3]Br2 (1) (dpamH = 2,2′-dipyridylamine) and the novel mixed-ligand complexes [Co(dpamH)2(bpo)]Br (2) and [Co(dpamH)2(opo)]Br (3), (bpo = the anion of 2-hydroxybenzophenone and opo = the anion of 2-hydroxy-4-methoxybenzophenone), in order to determine their thermal degradation in static air and dynamic nitrogen atmospheres. The cationic complexes were characterized by physicochemical methods, spectroscopy (FT-IR, UV–Vis), and single-crystal X-ray analysis, revealing octahedral coordination around cobalt(II) with chromophore CoN4O2, being chelated by one anionic 2-hydroxy-benzophenone ligand and two neutral dpamH molecules. The compounds crystallize as ethanol or ethanol/water solvates, with solvent molecules involved, to a different extent, in hydrogen bonding giving quite different packing modes and thus influencing their stability. The differences in crystal structures are reflected in thermal stabilities of the compounds. Thus, in the crystals of 3 ethanol is more weakly bound than in 2 and anticipate that the former one exhibit lower thermal stability, which is in agreement with the results found by TG–DTA. The thermal decomposition of the title complexes was found to be a multi-step decomposition related to the release of the solvent and ligand molecules, leading at 1,000 °C to pure metallic cobalt in nitrogen atmosphere, while in air atmosphere to the expected cobalt oxides.