Surprising Complexity of the [Gd(AAZTA)(H2O)2]− Chelate Revealed by NMR in the Frequency and Time Domains
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Surprising Complexity of the [Gd(AAZTA)(H2O)2]− Chelate Revealed by NMR in the Frequency and Time DomainsDate
2021-12-10Citation
Lalli, D.; Carniato, F.; Tei, L.; Platas-Iglesias, C.; Botta, M. Surprising Complexity of the [Gd(AAZTA)(H 2 O) 2 ] − Chelate Revealed by NMR in the Frequency and Time Domains. Inorg. Chem. 2022, 61 (1), 496–506. https://doi.org/10.1021/acs.inorgchem.1c03194.
Abstract
[Abstract] Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]− (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]− complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal–water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]−, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series.
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Atribución 3.0 España
ISSN
1520-510X
0020-1669
0020-1669