Fe(III) is a common miscreant released into our ecosystem from various industrial and anthropogenic activities which when in excess interferes with human health. A plethora of sensors based on various...

Fe(II) and Ni(II) paraCEST contrast agents containing the di-pyridine macrocyclic ligand 2,2′,2″-(3,7,10-triaza-1,5(2,6)-dipyridinacycloundecaphane-3,7,10triyl)triacetamide (DETA) are reported here. Both [Fe(DETA)] 2+ and [Ni-(DETA)] 2+ complexes were structurally characterized. Crystallographic data revealed the seven-coordinated distorted pentagonal bipyramidal geometry of the [Fe-(DETA)]•(BF 4 ) 2 •MeCN complex with five coordinated nitrogen atoms from the macrocyclic ring and two coordinated oxygen atoms from two amide pendant arms. The [Ni(DETA)]•Cl 2 •2H 2 O complex was six-coordinated in nature with a distorted octahedral geometry. Four coordinated nitrogen atoms were from the macrocyclic ring, and two coordinated oxygen atoms were from two amide pendant arms.[Fe(DETA)] 2+ exhibited well-resolved sharp proton resonances, whereas very broad proton resonances were observed in the case of [Ni(DETA)] 2+ due to the long electronic relaxation times. The CEST peaks for the [Fe(DETA)] 2+ complex showed one highly downfield-shifted and intense peak at 84 ppm with another shifted but less intense peak at 28 ppm with good CEST contrast efficiency at body temperature, whereas [Ni(DETA)] 2+ showed only one highly shifted intense peak at 78 ppm from the bulk water protons. Potentiometric titrations were performed to determine the protonation constants of the ligand and the thermodynamic stability constant of the [M(DETA)] 2+ (M = Fe, Co, Ni, Cu, Zn) species at 25.0 °C and I = 0.15 mol•L −1 NaClO 4 . Metal exchange studies confirmed the stability of the complexes in acidic medium in the presence of physiologically relevant anions and an equimolar concentration of Zn(II) ions.

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A summary of azabenzene-based ligands, having one to four N atoms, and their binding modes with different metals ions and magnetic properties are highlighted in this article based on recent publications.

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