Study of paraCEST response on six-coordinated Co(II) and Ni(II) complexes of a pyridine-tetraamide-based ligand.

This study highlights the successful synthesis of a potential ligand, 2,2',2'',2'''-((pyridine-2,6-diylbis(methylene))bis(azanetriyl))tetraacetamide (PATA), along with its corresponding Co(II) and Ni(II) complexes for paraCEST-based agents. X-ray diffraction data confirmed that both the complexes are six coordinated with distorted octahedral geometries, but only the [Co(PATA)] complex has a good structural feature to show paraCEST activity. After a thorough characterization of the ligand and both of its complexes, various studies, including solution-state magnetic properties, redox properties, temperature, and pH variation studies, were carried out. [Co(PATA)] remained inert in the presence of competing ions, under acidic conditions, at high temperatures, and in the physiological pH range. The paraCEST response of [Co(PATA)] has been measured in the presence of HEPES buffer medium, and a high paraCEST feature was discovered at both 37 and 25 °C. The pH variation paraCEST studies were carried out and the exchange rate constant of the probe at 37 and 25 °C was also determined. However, due to the fast exchange of water protons, the [Ni(PATA)(OH)] complex remained inactive in the CEST process.