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Article Dans Une Revue Journal of the American Chemical Society Année : 2009

Macrocyclic Receptor Exhibiting Unprecedented Selectivity for Light Lanthanides

Adrian Roca-Sabio
  • Fonction : Auteur
Marta Mato-Iglesias
  • Fonction : Auteur
David Esteban-Gomez
  • Fonction : Auteur
Andres de Blas
  • Fonction : Auteur
Carlos Platas-Iglesias
Teresa Rodriguez-Blas
  • Fonction : Auteur

Résumé

We report a new macrocyclic ligand, N, N'-bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6), designed for complexation of lanthanide ions in aqueous solution. Potentiometric measurements evidence an unprecedented selectivity of bp18c6 for the large Ln(III) ions. Among the different Ln(III) ions, La-III and Ce-III show the highest log K-ML values, with a dramatic drop of the stability observed from Ce-III to Lu-III as the ionic radius of the Ln(III) ions decreases (log K-CeL - log K-LuL = 6.9). The X-ray crystal structures of the Gd-III and Yb-III complexes show that the metal ion is directly bound to the 10 donor atoms of the bp18c6 ligand. The structure of the complexes in solution has been investigated by H-1 and C-13 NMR spectroscopy, as well as by theoretical calculations performed at the DFT (B3LYP) level. Our results indicate that a conformational change occurs around the middle of the lanthanide series: for the larger Ln(III) ions the most stable conformation is Delta(delta lambda delta)(delta lambda delta), while for the smallest Ln(III) ions (Gd-Lu) our calculations predict the Delta(lambda delta lambda)(lambda delta lambda) form being the most stable one. This structural change was confirmed by the analysis of the Ce-III-, Pr-III-, and Yb-III-induced paramagnetic H-1 shifts. The selectivity that bp18c6 shows for the large Ln(III) ions can be attributed to a better fit between the light Ln(III) ions and the relatively large crown fragment of the ligand. Indeed, our DFT calculations indicate that the interaction between the Ln(III) ion and several donor atoms of the crown moiety is weakened as the ionic radius of the metal ion decreases.
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Dates et versions

hal-00525299 , version 1 (11-10-2010)

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Citer

Adrian Roca-Sabio, Marta Mato-Iglesias, David Esteban-Gomez, Éva Tóth, Andres de Blas, et al.. Macrocyclic Receptor Exhibiting Unprecedented Selectivity for Light Lanthanides. Journal of the American Chemical Society, 2009, 131 (9), pp.3331-3341. ⟨10.1021/ja808534w⟩. ⟨hal-00525299⟩
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