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Cationic cyclometallated iridium(III) complexes with substituted 1,10-phenanthrolines: the role of the cyclometallated moiety on this new class of complexes with interesting luminescent and second order non linear optical properties

  • Claudia Dragonetti
  • Stefania Righetto
  • Dominique Roberto
  • Adriana Valore
  • Tiziana Benincori
  • Francesco Sannicolò
  • Filippo De Angelis
  • Simona Fantacci
Article

Abstract

The luminescence and second order non linear optical (NLO) response of [Ir(ttpy)2(5-R-1,10-phen)][PF6] (ttpy = cyclometallated 3′-(2-pyridil)-2,2′:5′,2″-terthiophene, phen = phenanthroline; R = Me, NO2) and [Ir(pq)2(5-R-1,10-phen)][PF6] (pq = cyclometallated 2-phenylquinoline) have been investigated experimentally in CH2Cl2 solution and compared with that of [Ir(ppy)2(5-R-1,10-phen)][PF6] (ppy = cyclometallated 2-phenylpyridine), characterized by one of the highest second order NLO response ever reported for a metal complex. Substitution of ppy with the more π-delocalized pq does not affect significantly the luminescence and NLO properties. A slightly lower NLO response and a much poorer luminescence is observed for the related complexes with ttpy. In these complexes, DFT/TDDFT calculations show that the presence of ttpy induces a significant downshift of the HOMO energy, compared to ppy and pq. The NLO response is dominated by intense MLCT excited states, which are also assigned as originating the emission.

Keywords

Phen High Occupied Molecular Orbital Phen Ligand Terthiophene High Occupied Molecular Orbital Orbital 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

We thank deeply Elisa Tordin for experimental help in EFISH measurements. This work was supported by MIUR (FIRB 2003) and by CNR (PROMO 2006).

References

  1. 1.
    R.C. Evans, P. Douglas, C. Winscom, Coord. Chem. Rev. 250, 2093 (2006)CrossRefGoogle Scholar
  2. 2.
    (a) J. Zyss, Molecular Nonlinear Optics: Materials, Physics and Devices. (Academic Press, Boston, 1994); (b) D.M. Roundhill, J.P. Fackler Jr. (eds.), Optoelectronic Properties of Inorganic Compounds (Plenum Press, New York, 1999)Google Scholar
  3. 3.
    For example see (a) D.R. Kanis, P.G. Lacroix, M.A. Ratner, T.J. Marks, J. Am. Chem. Soc. 116, 10089 (1994); (b) J. Heck, S. Dabek, T. Meyer-Friedrichsen, H. Wong, Coord. Chem. Rev. 190192, 1217 (1999); (c) H. Le Bozec, T. Renouard, Eur. J. Inorg. Chem. 2, 229 (2000); (d) P.G. Lacroix, Eur. J. Inorg. Chem. 2, 339 (2001); (e) S. Di Bella, Chem. Soc. Rev. 30, 355 (2001); (f) B.J. Coe, in Comprehensive Coordination Chemistry II, vol. 9, ed. by J.A. McCleverty, T.J. Meyer (Elsevier Pergamon, Oxford, UK, 2004), pp. 621–687; (g) B.J. Coe and N.R.M. Curati, Comments Inorg. Chem. 25, 147 (2004); (h) E. Cariati, M. Pizzotti, D. Roberto, F. Tessore, R. Ugo, Coord. Chem. Rev. 250, 1210 (2006); (i) B.J. Coe, Acc. Chem. Res. 39, 383 (2006)Google Scholar
  4. 4.
    C. Dragonetti, L. Falciola, P. Mussini, S. Righetto, D. Roberto, R. Ugo, A. Valore, F. De Angelis, S. Fantacci, A. Sgamellotti, M. Ramon, M. Muccini, Inorg. Chem. 46, 8533 (2007)PubMedCrossRefGoogle Scholar
  5. 5.
    C. Dragonetti, S. Righetto, D. Roberto, R. Ugo, A. Valore, S. Fantacci, A. Sgamellotti, F. De Angelis, Chem. Comm. 4116 (2007)Google Scholar
  6. 6.
    T.T. Dang, N. Rasool, T.T. Dang, H. Reinke, P. Langer, Tetrahedron Lett. 48, 845 (2007); J.H. Velez, F.R. Diaz, M.A. del Valle, T.C. Bernede, G.A. East, J. Appl. Polym. Sci. 102, 5314 (2006)Google Scholar
  7. 7.
    S. Sprouse, K.A. King, P.J. Spellane, R.J. Watts, J. Am. Chem. Soc. 106, 6647 (1984)CrossRefGoogle Scholar
  8. 8.
    I. Ledoux, J. Zyss, J. Chem. Phys. 73, 203 (1982)CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2008

Authors and Affiliations

  • Claudia Dragonetti
    • 1
    • 2
  • Stefania Righetto
    • 1
    • 2
  • Dominique Roberto
    • 1
    • 2
    • 3
  • Adriana Valore
    • 1
    • 2
  • Tiziana Benincori
    • 4
  • Francesco Sannicolò
    • 5
    • 2
  • Filippo De Angelis
    • 6
  • Simona Fantacci
    • 6
  1. 1.Dipartimento di Chimica Inorganica, Metallorganica e AnaliticaUniversità di MilanoMilanoItaly
  2. 2.UdR dell’INSTM di MilanoMilanoItaly
  3. 3.ISTM-CNRMilanoItaly
  4. 4.Dip. Scienze Chimiche ed Ambientali Università dell’InsubriaComoItaly
  5. 5.Dip. Chimica Organica e Industriale dell’Università di MilanoMilanoItaly
  6. 6.ISTM-CNRPerugiaItaly

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