Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Luminescence and Crystal-Field Analysis of Europium and Terbium Complexes with Oxydiacetate and 1,10-Phenanthroline

  • Kang, Jun-Gill (Department of Chemistry, Chungnam National University) ;
  • Kim, Tack-Jin (Department of Chemistry, Chungnam National University)
  • Published : 2005.07.20
Download PDF
⟨ Previous Next ⟩

Abstract

Photoluminescence (PL) spectra of Eu(III) and Tb(III) complexes with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and with homoleptic ODA reveal characteristic line-splitting at 10 K, depending on the site-symmetry of the lanthanide ion in the complex. The energy-level schemes of the $^7F_J$ states and the emitting levels for Eu(III) and Tb(III) ions have been proposed by simulating the line splitting in the framework of crystal-field Hamiltonian. The sets of refined crystal-field parameters for the experimentally determined sitesymmetry satisfactorily reproduce the experimental energy-level schemes. In addition, the PL quantum yield and the decay time were determined at room temperature. The PL quantum yields of [$Eu(ODA){\cdot}(phen){\cdot}4H_2O]^+$ and [Tb$(ODA){\cdot}(phen){\cdot}4H_2O]^+$ in the crystalline state (Q = 17.7 and Q = 56.6%, respectively) are much greater than those of [Eu($ODA)_3]^{3-}and\;[Tb(ODA)_3]^{3-}$(Q = 1.1 and Q = 1.3, respectively), due to the energy transfer from phen to the lanthanide ion. In the aqueous state, the relaxation of the phen moiety due to the solvent results in the reduction of the quantum yield and the shortening of the lifetime.

Keywords

References

  1. Richardson, F. S. Chem. Rev. 1982, 82, 541 https://doi.org/10.1021/cr00051a004
  2. Bünzli, J.-C. G. Lanthanide Probes in Life, Chemical and Earth Sciences; Bunzli, J.-C. G.; Choppin, G. R., Eds.; Elsevier: Amsterdam, Oxford, New York, Tokyo, 1989; Chapter 7
  3. McGehee, M. D.; Bergstedt, T. B.; Zhang, C.; Saab, A. P.; O'Regan, M. B.; Bazan, G. C.; Srdanov, V. I.; Heeger, A. J. Adv. Mater. 1999, 11, 1349 https://doi.org/10.1002/(SICI)1521-4095(199911)11:16<1349::AID-ADMA1349>3.0.CO;2-W
  4. de Sa, G. F.; Malta, O. L.; de Mello, Donega, C.; Simas, A. M.; Longo, R. L.; Sata-Cruz, P. A.; da Silva, E. F. Jr. Coord. Chem. Rev. 2000, 196, 165 https://doi.org/10.1016/S0010-8545(99)00054-5
  5. Zheng, Y.; Fu, L.; Zhou, Y.; Yu, J.; Yu, Y.; Wang, S.; Zhang, H. J. Mater. Chem. 2002, 12, 919 https://doi.org/10.1039/b110373c
  6. Fronczek, F. R.; Banerjee, A. K.; Watkins, S. F.; Schwartz, R. W. Inorg. Chem. 1981, 20, 2745 https://doi.org/10.1021/ic50222a080
  7. Albin, M.; Whittle, R. R.; De, W.; Horrocks, W. Jr., Inorg. Chem. 1985, 24, 4591 https://doi.org/10.1021/ic00220a032
  8. Schoene, K. A.; Quagliano, J. R.; Richardson, F. S. Inorg. Chem. 1991, 30, 3803 https://doi.org/10.1021/ic00020a007
  9. Metcalf, D. H.; Hopkins, T. A.; Richardson, F. S. Inorg. Chem. 1995, 34, 4868 https://doi.org/10.1021/ic00123a023
  10. Kang, J.-G.; Kim, T.-J.; Park K. S.; Kang, S. K. Bull. Korean Chem. Soc. 2004, 25, 337
  11. Kim, K.-B.; Kim, Y.-I.; Chun, H.-G.; Cho, T.-Y.; Jung, J.-S.; Kang, J.-G. Chem. Mater. 2002, 14, 5045 https://doi.org/10.1021/cm020592f
  12. de Mello, J. C.; Wittmann, H. F.; Friend, R. H. Adv. Mater. 1997, 9, 230 https://doi.org/10.1002/adma.19970090308
  13. Kang, J.-G.; Kim, T.-J.; Kang, H.-J.; Kang, S. K. J. Photochem. Photobio. A 2005 (in press)
  14. Handbook of the Physics and Chemistry of Rare Earths; Thompson, L. C., Eds.; North-Holland: Amsterdam and New York, 1979; V. 3, Chapter 25
  15. Mirochnik, A. G.; Bukvetskii, B. V.; Zhikhareva, P. A.; Karasev, V. E. Russ. J. Coord. Chem. 2001, 27, 443 https://doi.org/10.1023/A:1011352128346
  16. Wybourne, B. G. Spectroscopic Properties of Rare Earths; Interscience Pub.: New York, London, Sydney, 1965; Chapter 6
  17. Chang, N. C.; Gruber, J. B.; Leavitt, R. P.; Morrison, C. A. J. Chem. Phys. 1982, 76, 3877 https://doi.org/10.1063/1.443530
  18. Leavitt, R. P. J. Chem. Phys. 1982, 77, 1661 https://doi.org/10.1063/1.444088

Cited by

  1. Isostructural Series of Nine-Coordinate Chiral Lanthanide Complexes Based on Triazacyclononane vol.51, pp.15, 2012, https://doi.org/10.1021/ic300147p
  2. Sensitization of Visible and NIR Emitting Lanthanide(III) Ions in Noncentrosymmetric Complexes of Hexafluoroacetylacetone and Unsubstituted Monodentate Pyrazole vol.117, pp.44, 2013, https://doi.org/10.1021/jp403668j
  3. Experimental Measurement and Theoretical Assessment of Fast Lanthanide Electronic Relaxation in Solution with Four Series of Isostructural Complexes vol.117, pp.5, 2013, https://doi.org/10.1021/jp311273x
  4. O Chains vol.53, pp.14, 2014, https://doi.org/10.1021/ic500890r
  5. A new photoluminescent silica aerogel based on N-hydroxysuccinimide–Tb(III) complex vol.69, pp.1, 2014, https://doi.org/10.1007/s10971-013-3205-4
  6. )-containing metallo-supramolecular polymers: morphology control and optical wave-guiding properties vol.3, pp.34, 2015, https://doi.org/10.1039/C5TC01703C
  7. EuroTracker® dyes: design, synthesis, structure and photophysical properties of very bright europium complexes and their use in bioassays and cellular optical imaging vol.44, pp.11, 2015, https://doi.org/10.1039/C4DT02785J
  8. Emission of opal photonic crystals filled with europium and terbium vol.51, pp.6, 2015, https://doi.org/10.1134/S0020168515060060
  9. Efficient Layers of Emitting Ternary Lanthanide Complexes for Fabricating Red, Green, and Yellow OLEDs vol.54, pp.23, 2015, https://doi.org/10.1021/acs.inorgchem.5b01630
  10. Critical analysis of the limitations of Bleaney's theory of magnetic anisotropy in paramagnetic lanthanide coordination complexes vol.6, pp.3, 2015, https://doi.org/10.1039/C4SC03429E
  11. Location dependent coordination chemistry and MRI relaxivity, in de novo designed lanthanide coiled coils vol.7, pp.3, 2016, https://doi.org/10.1039/C5SC04101E
  12. -EDTA Functionalized Mixed Poly(diacetylene) Liposomes vol.6, pp.9, 2017, https://doi.org/10.1002/ajoc.201700158
  13. Europium(III) Catalyzed Recyclization of 2-(5-Isoxazolyl)phenol: Synthesis and Structure of Benzopyran Derivative vol.28, pp.12, 2005, https://doi.org/10.5012/bkcs.2007.28.12.2549
  14. Synthesis, luminescence and NMR studies of lanthanide (III) complexes with hexafluoroacetylacetone and phenanthroline. Part II vol.392, pp.None, 2005, https://doi.org/10.1016/j.ica.2012.06.032