| Summary: | Two pentadentate ligands built on the 2-aminomethylpiperidine structure and bearing two tertiary amino and three oxygen donors (three carboxylates in the case of AMPTA and two carboxylates and one phenolate for AMPDA-HB) were developed for Mn(II) complexation. Equilibrium studies on the ligands and the Mn(II) complexes were carried out using pH potentiometry, <sup>1</sup>H-NMR spectroscopy and UV-vis spectrophotometry. The Mn complexes that were formed by the two ligands were more stable than the Mn complexes of other pentadentate ligands but with a lower pMn than Mn(EDTA) and Mn(CDTA) (pMn for Mn(AMPTA) = 7.89 and for Mn(AMPDA-HB) = 7.07). <sup>1</sup>H and <sup>17</sup>O-NMR relaxometric studies showed that the two Mn-complexes were q = 1 with a relaxivity value of 3.3 mM<sup>−1</sup> s<sup>−1</sup> for Mn(AMPTA) and 3.4 mM<sup>−1</sup> s<sup>−1</sup> for Mn(AMPDA-HB) at 20 MHz and 298 K. Finally, the geometries of the two complexes were optimized at the DFT level, finding an octahedral coordination environment around the Mn<sup>2+</sup> ion, and MD simulations were performed to monitor the distance between the Mn<sup>2+</sup> ion and the oxygen of the coordinated water molecule to estimate its residence time, which was in good agreement with that determined using the <sup>17</sup>O NMR data.
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