Synthesis, characterization, and sorption activity of novel azo-colorants derived from phloroglucinol and antipyrine and their metal complexes

Two novel azo-colorants derived from phloroglucinol and antipyrine as well as 10 metal complexes with Co(ii), Ni(ii), Zn(ii), Cu(ii), and Cd(ii) were isolated and studied by a set of methods (1H, 13C NMR, IR, UV-VIS, EPR, X-ray structure determination). The azo-coupling of phloroglucinol with a 5-pyrazolone amino-derivative led to the isolation of a colorant H3L1 which was presented in the hydroxy-azo tautomeric form. At nitrosation of H3L1, the product H3L2 was isolated, which can be described as tri-oxo di-hydroxylamino hydrazone. According to the X-ray structure determination, the Cd-complex of H3L1 exhibited the dimeric form with two unionized organic ligands in the inner sphere. It was also found that chloride anions bridge two cadmium cations to form dimers. According to EPR spectra, the Cu-complex with H3L1 exhibited distorted tetragonal symmetry associated with the dx2-y2 ground state rather than dz2, and the corresponding Cu-H3L2 complex was described by a cubic symmetry of the coordination medium. Both H3L1, H3L2, and their metal complexes show coloristic activity towards wool, polyamide, and polyacetate fibers, which are strongly resistant towards UV-irradiation. The H3L2 compound possessed good sorption activity towards heavy metal cations from aqueous solutions of trace concentrations both under static and dynamic conditions. © The Royal Society of Chemistry.