Skip to main content
SpringerLink
Log in

Solvent-dependent dual-luminescence properties of a europium complex with helical π-conjugated ligands

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

A. europium(III) complex with a large it-conjugated helical ligand, tris(hexafluoroacetylacetonato)europium(III) bis((pentahelicenyl)diphenylphosphine oxide) (Eu(hfa)3(HPO)2), exhibits dual luminescence excited at the π-π* transition band. In this study, the solvent-dependent photophysical properties of Eu(hfa)3(HPO)2 are reported. The ground-state properties of the ligand and the Eu(III) complex are assessed from electronic absorption spectra, magnetic circular dichroism spectra, and density functional theory calculations. The excited-state properties of these compounds are evaluated using luminescence spectra, excitation spectra, luminescence lifetimes, and luminescence quantum yields depending on solvents, which are CHCl3, C2H5Br, C2H5I, CH3COCH3, and CD3COCD3. Under all of the examined conditions, the intensity ratios of dual luminescence originating from the ligand and the Eu(III) ion were strongly dependent on the properties of the solvent. The solvent dependence of the luminescence ratio is discussed in terms of the external heavy atom effect.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. H. Xu, Q. Sun, Z. An, Y. Wei and X. Liu, Electroluminescence from europium(m) complexes, Coord. Chem. Rev., 2015, 293-294, 228–249.

    Article  CAS  Google Scholar 

  2. F. Zinna, U. Giovanella and L. D. Bari, Highly circularly polarized electroluminescence from a chiral europium complex, Adv. Mater., 2015, 27, 1791–1795.

    Article  CAS  PubMed  Google Scholar 

  3. J. Zhuang, W. S. Lo, L. Zhou, Q. J. Sun, C. F. Chan, Y. Zhou, S. T. Han, Y. Yan, W. T. Wong, K. L. Wong and V. A. L. Roy, Photo-reactive charge trapping memory based on Iantha-nide complex, Sci. Rep., 2015, 5, 14998.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. J.-C. G. Biinzli and C. Piguet, Taking advantage of luminescent Ianthanide ions, Chem. Soc. Rev., 2005, 34, 1048–1077.

    Article  CAS  Google Scholar 

  5. J.-C. G. Biinzli, Lanthanide luminescence for biomedical analyses and imaging, Chem. Rev., 2010, 110, 2729–2755.

    Article  CAS  Google Scholar 

  6. N. Sayyadi, A. Care, R. E. Connally, A. C. Try, P. L. Bergquist and A. Sunna, Novel universal detection agent for time-gated luminescence bioimaging, Sci. Rep., 2016, 6, 27564.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  7. K. Miyata, T. Nakagawa, R. Kawakami, Y. Kita, K. Sugimoto, T. Nakashima, T. Harada, T. Kawai and Y. Hasegawa, Remarkable luminescence properties of Ianthanide complexes with asymmetric dodecahedron structures, Chem. -Eur. J., 2011, 17, 521–528.

    Article  CAS  PubMed  Google Scholar 

  8. K. Yanagisawa, T. Nakanishi, Y. Kitagawa, T. Seki, T. Akama, M. Kobayashi, T. Taketsugu, H. Ito, K. Fushimi and Y. Hasegawa, Seven-coordinate Iuminophores: brilliant luminescence of Ianthanide complexes with c3v geometrical structures, Eur. J. Inorg. Chem., 2015, 28, 4769–4774.

    Article  CAS  Google Scholar 

  9. M. Hatanaka and S. Yabushita, Mechanisms of f-f hypersensitive transition intensities of Ianthanide trihalide molecules: a spin-orbit configuration interaction study, Theor. Chem. Acc., 2014, 133, 1517.

    Article  CAS  Google Scholar 

  10. M. Hatanaka and S. Yabushita, Theoretical study on the f-f transition intensities of Ianthanide trihalide systems, J. Phys. Chem. A, 2009, 113, 12615–12625.

    Article  CAS  PubMed  Google Scholar 

  11. Y. Hasegawa, H. Kimura, K. Murakoshi, Y. Wada, J. H. Kim, N. Nakashima, T. Yamanaka and S. Yanagida, Enhanced emission of duterated tris(hexafluoroacetyIacetonato)neo-dymium(m) complex in solution by suppresion of radiationless transition via vibrational excitation, J. Phys. Chem., 1996, 100, 10201–10205.

    Article  CAS  Google Scholar 

  12. Y. Hasegawa, T. Ohkubo, K. Sogabe, Y. Kawamura, Y. Wada, N. Nakashima and S. Yanagida, Luminescence of novel neodymium sulfonylaminate complexes in organic media, Angew. Chem., Int. Ed., 2000, 39, 357–360.

    Article  CAS  Google Scholar 

  13. Y. Hasegawa, M. Yamamuro, Y. Wada, N. Kanehisa, Y. Kai and S. Yanagida, Luminescent polymer containing the EU(III) complex having fast radiation rate and high emission quantum efficiency, J. Phys. Chem. A, 2003, 107, 1697–1702.

    Article  CAS  Google Scholar 

  14. Y. Hirai, T. Nakanishi, Y. Kitagawa, K. Fushimi, T. Seki, H. Ito and Y. Hasegawa, Luminescent Eull I. coordination zippers linked with thiophene-based bridges, Angew. Chem., Int. Ed., 2016, 55, 12059–12062.

    Article  CAS  Google Scholar 

  15. O. Moudam, B. C. Rowan, M. Alamiry, P. Richardson, B. S. Richards, A. C. Jones and N. Robertson, Europium complexes with high total photoluminescence quantum yields in solution and in PMMA, Chem. Commun., 2009, 6649–6651.

    Google Scholar 

  16. E. E. S. Teotinio, G. M. Fett, H. F. Brito, W. M. Faustino, G. F. de Sa, M. C. F. C. Felinto and R. H. A. Santos, Evaluation of intramolecular energy transfer process in the Ianthanide(III) bis- and tris-(TTA) complexes: Photoluminescent and triboluminescent behavior, J. Lumin., 2008, 128, 190–198.

    Article  CAS  Google Scholar 

  17. J.-C. G. Biinzli, On the design of highly luminescent Ianthanide complexes, Coord. Chem. Rev., 2015, 293–294, 19–47.

    Article  CAS  Google Scholar 

  18. K. Binnemans, Interpretation of europium(m) spectra, Coord. Chem. Rev., 2015, 295, 1–45.

    Article  CAS  Google Scholar 

  19. C. Yang, L. M. Fu, Y. Wang, J. P. Zhang, W. T. Wong, X. C. Ai, Y. F. Qiao, B. S. Zou and L. L. Gui, A highly luminescent europium complex showing visible-light-sensitized red emission: direct observation of the singlet pathway, Angew. Chem., Int. Ed., 2004, 43, 5010–5013.

    Article  CAS  Google Scholar 

  20. L. M. Fu, X. C. Ai, M. Y. Li, X. F. Wen, R. Hao, Y. S. Wu, Y. Wang and J. P. Zhang, Role of Iigand-to-metal charge transfer state in nontriplet photosensitization of luminescent europium complex, J. Phys. Chem. A, 2010, 114, 4494–4500.

    Article  CAS  PubMed  Google Scholar 

  21. Y. Imai, T. Kawai and J. Yuasa, J. Off-on-off dual emission at visible and UV. wavelengths from carbazole functionalized β-diketonate europium(III) complex, J. Phys. Chem. A, 2016, 120, 4131–4138.

    Article  CAS  PubMed  Google Scholar 

  22. P. Coppo, M. Duati, V. N. Kozhevnikov, J. W. Hofstraat and L. Cola, White-light emission from an assembly comprising luminescent iridium and europium complexes, Angew. Chem., Int. Ed., 2005, 44, 1806–1810.

    Article  CAS  Google Scholar 

  23. M. A. El-Sayed, Spin-orbit coupling and the radiationless processes in nitrogen heterocyclics, J. Chem. Phys., 1963, 38, 2834–2838.

    Article  CAS  Google Scholar 

  24. M. Szymanski, A. Maciejewski and R. P. Steer, Concerning apparent intersystem crossing efficiencies in molecules with small S1- T1 energy gaps, J. Photochem. Photobiol., A, 1991, 57, 405–418.

    Article  CAS  Google Scholar 

  25. S. Lobsiger, M. Etinski, S. Blaser, H.-M. Frey, C. Marian and S. Leutwyler, Intersystem crossing rates of S1 state keto-amino cytosine at low excess energy, J. Chem. Phys., 2015, 143, 234301.

    Article  PubMed  CAS  Google Scholar 

  26. P. P. Lima, S. S. Nobre, R. O. Freire, S. A. Junior, L. Mafra, R. A. S. Ferreira, U. Pischel, O. L. Malta and L. D. Carlos, Energy transfer mechanisms in organic-inorganic hybrids incorporating europium(III): A. quantitative assessment by light emission spectroscopy, J. Phys. Chem. C, 2007, 111, 17627–17634.

    Article  CAS  Google Scholar 

  27. G. F. de Sa, O. L. Malta, C. de Mello Donega, A. M. Simas, R. L. Longo, P. A. Santa-Cruz and E. F. da Silva Jr., Spectroscopic properties and design of highly luminescent lanthanide coordination complexes, Coord. Chem. Rev., 2000, 196, 165–195.

    Article  Google Scholar 

  28. S. Omagari, T. Nakanishi, Y. Kitagawa, K. Fushimi, T. Seki, H. Ito, A. Meijerink and Y. Hasegawa, Critical role of energy transfer between terbium ions for suppression of back energy transfer in nonanuclear terbium clusters, Sci. Rep., 2016, 6, 37008.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Y. Kitagawa, R. Ohno, T. Nakanishi, K. Fushimi and Y. Hasegawa, Visible luminescent Ianthanide ions and a large π-conjugated Iigand system shake hands, Phys. Chem. Chem. Phys., 2016, 18, 31012–31016.

    Article  CAS  PubMed  Google Scholar 

  30. T. Hirose, N. Ito, H. Kubo, T. Sato and K. Matsuda, Fluorescence behavior of 5,10-disubstituted [5]helicene derivatives in solution and the effect of self-assembly on their radiative and non-radiative rate constants, J. Mater. Chem. C, 2016, 4, 2811–2819.

    Article  CAS  Google Scholar 

  31. K. Schmidt, S. Brovelli, V. Coropceanu, D. Beljonne, J. Cornil, C. Bazzini, T. Caronna, R. Tubino, F. Meinardi, Z. Shuai and J.-L. Bredas, Intersystem crossing processes in nonplanar aromatic heterocyclic molecules, J. Phys. Chem. A, 2007, 111, 10490–10499.

    Article  CAS  PubMed  Google Scholar 

  32. J. B. Birks, D. J. S. Birch, E. Cordemans and E. Vander Donckt, Fluorescence of the higher helicenes, Chem. Phys. Lett., 1976, 43, 33–36.

    Article  CAS  Google Scholar 

  33. M. Sapir and E. Vander Donckt, Intersystem crossing in the helicenes, Chem. Phys. Lett., 1975, 36, 108–110.

    Article  CAS  Google Scholar 

  34. K. Palewska and H. Chojnacki, Electronic spectra and luminescence properties of helicenes in crystalline matrices at 4.2 K, Mol. Cryst. Liq. Cryst, 1993, 229, 31–36.

    Article  CAS  Google Scholar 

  35. Y. Shimizu and T. Azumi, Mechanism of external heavy atom effect on intersystem crossing in fluid solutions. Analysis based on fluorescence decay data, J. Phys. Chem., 1982, 86, 22–26.

    Article  CAS  Google Scholar 

  36. S. Goretta, C. Tasciotti, S. Mathieu, M. Smet, W. Maes, Y. M. Chabre, W. Dehaen, R. Giasson, J.-M. Raimundo, C. R. Henry, C. Barth and M. Gingras, Expeditive syntheses of functionalized pentahelicenes and NC-AFM. on Ag(001), Org. Lett, 2009, 11, 3846–3849.

    Article  CAS  PubMed  Google Scholar 

  37. H. Kataoka, T. Nakanishi, S. Omagari, Y. Takabatake, Y. Kitagawa and Y. Hasegawa, Drastically improved durability and efficiency of silicon solar cells using hyper-stable Ianthanide coordination polymer beads, Bull. Chem. Soc. Jpn., 2016, 89, 103–109.

    Article  CAS  Google Scholar 

  38. C. T. Lee, W. T. Yang and R. G. Parr, Development of the colle-salvetti correlation-energy formula into a functional of the electron-density, Phys. Rev. B: Condens. Matter, 1988, 37, 785–789.

    Article  CAS  Google Scholar 

  39. A. D. Becke, Density-functional thermochemistry 0.3. The role of exact exchange, J. Chem. Phys., 1993, 98, 5648–5652.

    Article  CAS  Google Scholar 

  40. J. Mack, M. J. Stillman and N. Kobayashi, Application of MCD. spectroscopy to porphyrinoids, Coord. Chem. Rev., 2007, 251, 429–453.

    Article  CAS  Google Scholar 

  41. Y. Kitagawa, H. Segawa and K. Ishii, Magneto-chiral dichroism of organic compounds, Angew. Chem., Int. Ed., 2011, 50, 9133–9136.

    Article  CAS  Google Scholar 

  42. Y. Kitagawa, T. Miyatake and K. Ishii, Magneto-chiral dichroism of artificial light-harvesting antenna, Chem. Commun., 2012, 48, 5091–5093.

    Article  CAS  Google Scholar 

  43. T. Kinoshita, J. T. Dy, S. Uchida, T. Kubo and H. Segawa, Wideband dye-sensitized solar cells employing a phos-phine-coordinated ruthenium sensitizer, Nat. Photonics, 2013, 7, 535–539.

    Article  CAS  Google Scholar 

  44. W. J. Siebrand, Radiationless transitions in polyatomic molecules. I. Calculation of franck-condon factors, J. Chem. Phys., 1967, 46, 440–447.

    Article  CAS  Google Scholar 

  45. Fluorescence Stokes shift of the HPO. Iigand is 840 cm−1.29

Download references

Author information

Authors and Affiliations

  1. Faculty of Engineering, Hokkaido University, Kita-13 Jo, Nishi-8 Chome, Kita-ku, Sapporo, Hokkaido, 060-8628, Japan

    Yuichi Kitagawa, Takayuki Nakanishi, Koji Fushimi & Yasuchika Hasegawa

  2. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Kita-13 Jo, Nishi-8 Chome, Kita-ku, Sapporo, Hokkaido, 060-8628, Japan

    Ryohsuke Ohno

Authors
  1. Yuichi Kitagawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ryohsuke Ohno
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Takayuki Nakanishi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Koji Fushimi
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yasuchika Hasegawa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yuichi Kitagawa.

Additional information

Electronic supplementary information (ESI) available. See DOI: 10.1039/c7pp00007c

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kitagawa, Y., Ohno, R., Nakanishi, T. et al. Solvent-dependent dual-luminescence properties of a europium complex with helical π-conjugated ligands. Photochem Photobiol Sci 16, 683–689 (2017). https://doi.org/10.1039/c7pp00007c

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c7pp00007c

Search

Navigation