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Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy

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Abstract

Earlier the intramolecular inversion of the 18-crown-6 molecules was found in the complex ion pairs [Ln(ptfa)2 (18-crown-6)]+ [Ln(ptfa)4]− (H2O)4 where Ln = La(1), Ce (2), Pr (3), Nd (4), and ptfa is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione. In this work the peculiarities of the molecular structure and dynamics were studied for [Eu(ptfa)2 (18-crown-6)]+ [Eu(ptfa)4]− (H2O)4 (5) by NMR spectroscopy techniques. Through VT-NMR spectra analysis the temperature dependence was obtained for the rate constant. The free energy ΔG‡(320) of 18-crown-6 ring inversion activation was found to be 65 ± 5 kJ mol−1 for 5 in CDCl3. This result is comparable with the earlier data [S.P. Babailov and D.A. Mainichev: J. Inclusion Phenom. Macrocyclic Chem. 43, 187–193 (2002)] for complexes 2, 3, 4 in deuterated toluene (ΔG‡(320)=65 ± 9, 64 ± 9, 64 ± 9 kJ mol−1 respectively). It was found by relaxation NMR spectroscopy that the effective distance between Ln and protons of the crown molecule is 4.5 ± 0.2 Å. The analysis of structural parameters testifies that the crown ether and chelated anions are in the first coordination sphere of a Ln cation. Obtained geometrical parameters show that the complex cations of Eu, Ce and Pr have similar spatial structures.

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Authors and Affiliations

  1. Institute of Inorganic Chemistry SB RAS, pr. Lavrentyev, 3, Novosibirsk, 630090, Russia

    Sergey P. Babailov, Dmitry A. Mainichev & Lubov D. Nikulina

  2. Institute of Chemical Kinetics and Combustion SB RAS, Institutskaya, 3, Novosibirsk, 630090, Russia

    Svetlana S. Petrova

Authors
  1. Sergey P. Babailov
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  2. Dmitry A. Mainichev
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  3. Lubov D. Nikulina
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  4. Svetlana S. Petrova
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Correspondence to Sergey P. Babailov.

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Babailov, S.P., Mainichev, D.A., Nikulina, L.D. et al. Intramolecular Dynamics and Molecular Structure of Europium(III) Chelate Complexes with Crown Ethers as Studied by NMR Spectroscopy. J Incl Phenom Macrocycl Chem 51, 73–78 (2005). https://doi.org/10.1007/s10847-004-2385-5

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  • DOI: https://doi.org/10.1007/s10847-004-2385-5

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