Crystal structure and absorption spectroscopy of a dimeric neodymium(III) complex with triethylenetetraaminehexaacetic acid (H₆ttha), Na_0.5H_5.5[Nd₂(ttha)₂]·7.5NaClO₄·16.83H₂O

Abstract

The crystal structure and absorption spectra (IR, UV/VIS) have been determined for Na_0.5H_5.5[Nd₂(ttha)₂]· 7.5NaClO₄·16.83H₂O (H₆ttha = triethylenetetraaminehexaacetic acid). The structure consists of the complex dimer, perchlorate anions, sodium cations and water of hydration. Both neodymium(III) ions are nine-co-ordinate. Each ttha ligand is bonded to one Nd^III through four of its carboxyl oxygen atoms and three of its nitrogen atoms. Two carboxyl oxygen atoms are bonded to the other Nd^III, and the fourth nitrogen atom remains unco-ordinated. The co-ordination spheres of both Nd^III are essentially the same and may be defined as distorted tricapped trigonal prisms. Absorption spectra of a single crystal were measured at room and liquid-helium temperatures. The intensities of the f–f transitions were analysed on the basis of Judd–Ofelt theory. Comparison of the absorption spectra of [Nd(ttha)]^3– in solution to those of single crystals of Na₃[Nd(ttha)]· 2.5NaClO₄·7.617H₂O and Na_0.5H_5.5[Nd₂(ttha)₂]·7.5NaClO₄·16.83H₂O compounds allowed us to estimate the ratio of mono- to di-meric species in solution.

References

1. R. B. Lauffer, Chem. Rev., 1987, 87, 901.
2. M. F. Tweedle, in Lanthanide Probes in Life, Chemical and Earth Sciences, Theory and Practice, eds. J.-C. G. Bünzli and G. R. Choppin, Elsevier, Amsterdam, 1989, ch. 5, pp. 127–179.
3. G. R. Choppin, in Lanthanide Probes in Life, Chemical and Earth Sciences, Theory and Practice, eds. J.-C. G. Bünzli and G. R. Choppin, Elsevier, Amsterdam, 1989, ch. 1, pp. 1–41.
4. G. R. Choppin, J. Less-Common Met., 1993, 192, 256.
5. G. R. Choppin and K. M. Schaab, Inorg. Chim. Acta, 1996, 252, 299.
6. G. R. Choppin, P. A. Baisden and S. A. Khan, Inorg. Chem., 1979, 18, 1330.
7. J. A. Peters, Inorg. Chem., 1988, 27, 4686.
8. B. G. Jenkins and R. B. Laufer, Inorg. Chem., 1988, 27, 4730.
9. S. Aime and M. Botta, Inorg. Chim. Acta, 1990, 177, 101.
10. C. A. Chang, H. G. Brittain, J. Telser and M. F. Tweedle, Inorg. Chem., 1990, 29, 4468.
11. J. J. Stezowski and J. L. Hoard, Isr. J. Chem., 1984, 24, 323.
12. M. B. Inoue, M. Inoue and Q. Fernando, Inorg. Chim. Acta, 1995, 232, 203.
13. M. S. Konings, W. C. Dow, D. B. Love, K. N. Raymond, S. C. Quay and S. M. Rocklage, Inorg. Chem., 1990, 29, 1488.
14. E. Ehnebom and B. F. Pedersen, Acta Chem. Scand., 1992, 46, 126.
15. E. N. Rizkalla, G. R. Choppin and W. Cacheris, Inorg. Chem., 1993, 32, 582.
16. C. F. G. C. Geraldes, A. M. Urbano, M. A. Hoefnagel and J. A. Peters, Inorg. Chem., 1993, 32, 2426.
17. S. T. Frey, C. A. Chang, J. F. Carvalho, A. Varadarajan, L. M. Schultze, K. L. Pounds and W. DeW. Horrocks, jun., Inorg. Chem., 1994, 33, 2882.
18. S. J. Franklin and K. N. Raymond, Inorg. Chem., 1994, 33, 5794.
19. C. Paul-Roth and K. N. Raymond, Inorg. Chem., 1995, 34, 1408.
20. S. W. A. Bligh, A. H. M. S. Chowdhury, M. McPartlin, I. J. Scowen and R. A. Bulman, Polyhedron, 1995, 14, 567.
21. C. F. G. C. Geraldes, A. M. Urbano, M. C. Alpoim, A. D. Sherry, K.-T. Kuan, K. R. Rajagopalan, F. Maton and R. N. Muller, Magn. Reson. Imag., 1995, 13, 401.
22. E. Bovens, M. A. Hoefnagel, E. Boers, H. Lammers, H. van Bekkum and J. A. Peters, Inorg. Chem., 1996, 35, 7679.
23. P. R. Selvin, J. Jancarik, Min Li and Li-Wei Hung, Inorg. Chem., 1996, 35, 700.
24. S. Aime, F. Benetollo, G. Bombieri, S. Colla, M. Fasano and S. Paoletti, Inorg. Chim. Acta, 1997, 254, 63.
25. H. Gries and H. Miklautz, Physiol. Chem. Phys. Med. NMR, 1984, 16, 105.
26. W. P. Cacheris, S. C. Quay and S. M. Rocklage, Magn. Reson. Imag., 1990, 8, 467.
27. A. Yingst and A. E. Martell, J. Am. Chem. Soc., 1969, 91, 6927.
28. R. B. Gayhart and T. J. Moeller, Inorg. Nucl. Chem., 1977, 39, 49.
29. T. J. Wenzel, M. E. Ashley and R. E. Sievers, Anal. Chem., 1982, 54, 615.
30. R. C. Holz and W. DeW. Horrocks, jun., Inorg. Chim. Acta, 1990, 171, 193.
31. H. G. Brittain, J. Coord. Chem., 1990, 21, 295.
32. A. Mondry and J. P. Riehl, Acta Phys. Polon. A, 1993, 84, 969.
33. A. Mondry, S. C. J. Meskers and J. P. Riehl, J. Lumin., 1994, 62, 17.
34. A. Mondry and P. Starynowicz, Inorg. Chem., 1997, 36, 1176.
35. R. Ruloff, P. Prokop, J. Sieler, E. Hoyer and L. Beyer, Z. Naturforsch., Teil B, 1996, 51, 963.
36. R. Y. Wang, J. R. Li, T. Z. Jin, G. X. Xu, Z. Y. Zhou and X. G. Zhou, Polyhedron, 1997, 16, 1361: 2037.
37. D. F. Chen, W. C. Yang, R. Y. Wang and T. Z. Jin, Acta Chim. Sin., 1997, 55, 672.
38. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
39. G. M. Sheldrick, SHELXL 93, Program for Crystal Structure Refinement, University of Göttingen, 1993.
40. International Tables for X-Ray Crystallography, ed. A. J. C. Wilson, Kluwer, Dordrecht, 1992, vol. C.
41. B. R. Judd, Phys. Rev., 1962, 127, 750.
42. G. S. Ofelt, J. Chem. Phys., 1962, 37, 511.
43. W. T. Carnall, P. R. Fields and K. Rajnak, J. Phys. Chem., 1968, 49, 4424.
44. C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
45. M. G. B. Drew, Coord. Chem. Rev., 1977, 24, 179.
46. R. E. Sievers and J. C. Bailar, Inorg. Chem., 1962, 1, 174.
47. P. Starynowicz and K. Bukietyńska, Polyhedron, 1994, 13, 109.