Paramagnetic properties and molecular structure of coordination saturated inclusive lanthanide complexes with 18-crown-6 using NMR

Original Article


Earlier NMR spectra of lanthanide complexes [Ln(18-crown-6)(NO3)3] have been analyzed by us (Babailov in Inorg Chem 51(3):1427–1433, 2012), where Ln3+ = La3+ (I), Ce3+ (II), Pr3+ (III) and Nd3+ (IV). The NMR signal assignment and conformational molecular dynamic have been found by 1D NOE and relaxation spectroscopy as well as on 2D NOESY and EXSY experiments at 170 K. In the present paper the 1H NMR method is used to study the features of paramagnetic properties of complexes IIV and [Eu(18-crown-6)(NO3)3] (V) at ambient temperature. The investigation was carried out by special method based on analysis of Δδ/<Sz> on k(Ln)/<Sz> (where k(Ln) is Bleaney’s constant, Δδ is paramagnetic contribution to the lanthanide-induced shifts). The obtained results indicate that the structure of the complexes (in CDCl3 and CD2Cl2) are very similar.


Complexes of lanthanides Crown ethers 18-Crown-6 Structure similarity Paramagnetic lanthanide-induced shifts NMR 



The study was carried out with partial financial support of the Russian Foundation for Basic Research (Grants Nos. 11-03-00197-a and N 14-03-00386-a).


  1. 1.
    Peters, J.A., Huskens, J., Raber, D.J.: Lanthanide induced shifts and relaxation rate enhancements. Prog. Nucl. Magn. Reson. Spectrosc. 28, 283 (1996)CrossRefGoogle Scholar
  2. 2.
    Otting, G.: Prospects for lanthanides in structural biology by NMR. J. Biomol. NMR 42, 1–9 (2008)CrossRefGoogle Scholar
  3. 3.
    Yamamoto, K., Vivekanandan, S., Ramamoorthy, A.: Data acquisition from bicelles containing a membrane-associated peptide at natural-abundance. J. Phys. Chem. B 115, 12448–12455 (2011)CrossRefGoogle Scholar
  4. 4.
    Harman, M.E., Hart, F.A., Hursthouse, M.B., Moss, G.P., Raithby, P.R.: 12-coordinated crown ether complex of lanthanium. J. Chem. Soc. Chem. Commun. 11, 396 (1976)CrossRefGoogle Scholar
  5. 5.
    Bunzli, J.C.G., Wessner, D.: Complexes of lanthanide nitrate with 15-crown-5 and 18-crown-6 ethers. Helv. Chim. Acta 61, 1454 (1978)CrossRefGoogle Scholar
  6. 6.
    Rigault, S., Piguet, C., Bunzli, J.C.G.: Lanthanide-containing molecular and supramolecular functional assemblies. J. Chem. Soc. Dalton Trans. 31, 2045 (2000)CrossRefGoogle Scholar
  7. 7.
    Piguet, C., Geraldes, C.F.G.C.: In: Gschneidner, K.A., Bünzli, J.-C.G., Pecharsky, V.K. (eds.) Handbook on the Physics and Chemistry of Rare Earths, vol. 33, pp. 353–463. Elsevier Science, Amsterdam (2003)Google Scholar
  8. 8.
    Babailov, S.P.: Lanthanide paramagnetic probes for NMR spectroscopic studies of molecular conformational dynamics in solution. Applications to macrocyclic molecules. Prog. Nucl. Magn. Reson. Spectrosc. 1, 1 (2008)CrossRefGoogle Scholar
  9. 9.
    Babailov, S.P., Krieger, J.H., Gabuda, S.P.: 1H NMR study of the dynamic structure of nitrate complexes of lanthanides with 18-crown-6. Bull. Acad. Sci. SSSR Div. Chem. Sci. 11, 2661 (1990)Google Scholar
  10. 10.
    Babailov, S.P.: Lanthanide paramagnetic probes for NMR spectroscopic studies of fast molecular conformational dynamics and temperature control. Effective six-site proton exchange in 18-crown-6 by exchange spectroscopy. Inorg. Chem. 51(3), 1427–1433 (2012)CrossRefGoogle Scholar
  11. 11.
    Babailov, S.P., Krieger, J.H., Martynova, T.N., Nikulina, L.D., Polyanskaya, T.M.J.: NMR study of mixed-ligand complexes of lanthanides. Lanthanide-induced enhancement in the spin-lattice relaxation. Struct. Chem. (USSR) 29, 80 (1988)Google Scholar
  12. 12.
    Babailov, S.P., Krieger, J.H., Martynova, T.N., Nikulina, L.D.J.: Study the geometric structure of mixed-ligand complexes of the heaviest lanthanides by NMR and NMR relaxation. Struct. Chem. (USSR) 31, 44 (1990)Google Scholar
  13. 13.
    Frenzel, T.T.K., Kobler, S.R.B., Bauer, H.P.J., Weinmann, H.J.: Noninvasive temperature measurement in vivo using a temperature-sensitive lanthanide complex and 1H magnetic resonance spectroscopy. Magn. Reson. Med. 35, 364 (1996)CrossRefGoogle Scholar
  14. 14.
    Aime, S.B.M., Fasano, M.T.E., Kinchesh, P.C.L., Paleari, L.: A new ytterbium chelate as contrast agent in chemical shift imaging and temperature sensitive probe for MR spectroscopy. Magn. Reson. Med. 35, 648–651 (1996)CrossRefGoogle Scholar
  15. 15.
    Babailov, S.P.: Intermolecular dynamics and paramagnetic properties of ethylenediaminetetraacetate complexes with the yttrium subgroup rare earth elements using NMR. Magn. Reson. Chem. 50(12), 793 (2012). doi: 10.1002/mrc.3884 CrossRefGoogle Scholar
  16. 16.
    Babailov, S.P., Kokovkin, V.V., Stabnikov, P.A.: Paramagnetic properties and kinetics of chelation of praseodymium (III) and holmium (III) cations with EDTA in aqueous solution. J. Struct. Chem. 51(4), 682 (2010)CrossRefGoogle Scholar
  17. 17.
    Babailov, S.P., Nikulina, L.D., Krieger, J.H.: Intramolecular dynamics of lanthanide(III) tetraoxadiaza macrocycle complexes in solution as studied by NMR. J. Incl. Phenom. Macrocycl. Chem. 43, 25–29 (2002)CrossRefGoogle Scholar
  18. 18.
    Babailov, S.P., Nikulina, L.D.: NMR studies of mixed-ligand lanthanide complexes in solution: pseudorotation and ring inversion of 18-crown-6 molecule in cerium subgroup chelates. J. Incl. Phenom. Macrocycl. Chem. 51(1), 103–109 (2005)CrossRefGoogle Scholar
  19. 19.
    Babailov, S.P., Coutsolelos, A.G., Dikiy, A., Spyroulias, G.A.: Intramolecular dynamics of asymmetric lanthanide(III) porphyrin sandwich complexes in solution. Eur. J. Inorg. Chem. 1, 303–306 (2001)CrossRefGoogle Scholar
  20. 20.
    Babailov, S.P., Mainichev, D.A.: Studies of mixed-ligand lanthanide(III) complexes. Peculiarities of molecular structure, dynamics and paramagnetic properties for cerium subgroup chelates with crown ethers. J. Incl. Phenom. 43, 187 (2002)CrossRefGoogle Scholar
  21. 21.
    Babailov, S.P., Krieger, J.H.: NMR methods for molecular structure studies of paramagnetic lanthanide complexes in solutions: applications to crown ether complexes. Russ. J. Struct. Chem. 39, 714 (1998)CrossRefGoogle Scholar
  22. 22.
    Babailov, S.P.: Nanosized thermometric NMR sensors based on double-decker paramagnetic lanthanide(III) complexes with porphyrins for temperature determination in solutions. Macroheterocycles 3, 209 (2010)Google Scholar
  23. 23.
    Bleaney, B.: Nuclear magnetic resonance shifts due to lanthanide ions. J. Magn. Reson. 25, 91 (1972)Google Scholar
  24. 24.
    De Boer, J.W.M., Sakkers, P.J.D., Hilbers, C.W., De Boer, M.: Lanthanide shift reagents. J. Mag. Reson. 25, 455 (1977)Google Scholar
  25. 25.
    Babailov, S.P.: NMR studies of photo-induced chemical exchange. Magn. Reson. Chem. 50(12), 793–799 (2012)CrossRefGoogle Scholar
  26. 26.
    Reilley, C.N., Good, B.W., Allendoerfer, R.D.: Separation of contact and dipolar lanthanide induced nuclear magnetic resonance shifts: evaluation and application of some structure independent methods. Anal. Chem. 48(11), 1446–1458 (1976)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  1. 1.A.V.Nikolaev’s Institute of Inorganic Chemistry, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Novosibirsk State UniversityNovosibirskRussia

Personalised recommendations