Skip to main content
SpringerLink
Log in

Synthesis and photophysical properties of IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes containing bipyrimidines as bridging ligands

  • Published:
Science in China Series B: Chemistry Aims and scope Submit manuscript

Abstract

Bipyrimidines have been chosen as (N∧N)(N∧N) bridging ligands for connecting metal centers. IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O. The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration. The obvious quenching of visible emission from IrIII complex in the IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes indicates that energy transfer occurred from IrIII center to lanthanides. NIR emissions from NdIII, YbIII, and ErIII were obtained under the excitation of visible light by selective excitation of the IrIII-based chromophore. It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdIII, YbIII, and ErIII.

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. Gunnlaugsson T, Leonard J P, Sénéchal K, Harte A J. pH responsive Eu(III)-phenanthroline supramolecular conjugate: Novel “off-on-off” luminescent signaling in the physiological pH range. J Am Chem Soc, 2003, 125: 12062–12063

    Article  CAS  Google Scholar 

  2. Xu Y Y, Hemmilä I A. Analytical application of the co-fluorescence effect in detection of europium, terbium, samarium and dysprosium with time-resolved fluorimetry. Talanta, 1992, 39: 759–763

    Article  CAS  Google Scholar 

  3. Weibel N, Charbonnière L J, Guardigli M, Roda A, Ziessel R. Engineering of highly luminescent lanthanide tags suitable for protein labeling and time-resolved luminescence imaging. J Am Chem Soc, 2004, 126: 4888–4896

    Article  CAS  Google Scholar 

  4. Werts M H V, Duin M A, Hofstraat J W, Verhoeven J W. Bathochromicity of Michler’s ketone upon coordination with lanthanide(III) beta-diketonates enables efficient sensitisation of Eu3+ for luminescence under visible light excitation. Chem Commun, 1999: 799–800

  5. Yang C, Fu L M, Wang Y, Zhang J P, Wong W T, Ai X C, Qiao Y F, Zou B S, Gui L L. 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 

  6. Van Deun R, Nockemann P, Fias P, Van Hecke K, Van Meervelt L, Binnemans K. Visible light sensitisation of europium(III) luminescence in a 9-hydroxyphenal-1-one complex. Chem Commun, 2005: 590–592

  7. Bünzli J C G, Piguet C. Taking advantage of luminescent lanthanide ions. Chem Soc Rev, 2005, 34: 1048–1077

    Article  Google Scholar 

  8. Ward M D. Transition-metal sensitised near-infrared luminescence from lanthanides in d-f heteronuclear arrays. Coordin Chem Rev, 2007, 251: 1663–1677

    Article  CAS  Google Scholar 

  9. Chen F F, Bian Z Q, Liu Z W, Nie D B, Chen Z Q, Huang C H. Highly efficient sensitized red emission from europium (III) in Ir-Eu bimetallic complexes by 3MLCT energy transfer. Inorg Chem, 2008, 47: 2507–2513

    Article  CAS  Google Scholar 

  10. Chen F F, Bian Z Q, Lou B, Ma E, Liu Z W, Nie D B, Chen Z Q, Bian J, Chen Z N, Huang C H. Sensitised near-infrared emission from lanthanides using an iridium complex as a ligand in heteronuclear Ir2 Ln arrays. Dalton Trans, 2008: 5577–5583

  11. Li D, Chen F F, Bian Z Q, Liu Z W, Zhao Y L, Huang C H. Sensitized near-infrared emission of YbIII from an IrIII-YbIII bimetallic complex. Polyhedron, 2009, 28: 897–902

    Article  CAS  Google Scholar 

  12. Iftikhar K, Sayeed M, Ahmad N. Mixed-ligand complexes of trivalent lanthanide ions with beta-diketones and heterocyclic amines. Inorg Chem, 1982, 21: 80–84

    Article  CAS  Google Scholar 

  13. Sano T, Fujita M, Fujii T, Hamada Y, Shibata K, Kuroki K. Novel europium complex for electroluminescent devices with sharp red emission. Jan J Appl Phys Pt 1, 1995, 34: 1883–1887

    Article  CAS  Google Scholar 

  14. Yajima S, Hasegawa Y. Variation of thermodynamic parameters in the adduct formation of beta-diketonato chelates with 1,10-phenanthroline across the lanthanoid series. Bull Chem Soc Jpn, 1998, 71: 2825–2829

    Article  CAS  Google Scholar 

  15. Kertes A S, Kassierer E F. Thermochemistry of lanthanide complexes in thenoyltrifluoroacetone-bipyridyl system. Inorg Chem, 1972, 11: 2108–2111

    Article  CAS  Google Scholar 

  16. Shavaleev N M, Bell Z R, Ward M D. A simple, general synthesis of mixed d-f complexes containing both {Re(CO)3Cl(diimine)} and lanthanide-tris(beta-diketonate) luminophores linked by bis-diimine bridging ligands. J Chem Soc Dalton Trans, 2002: 3925–3927

  17. Shavaleev N M, Accorsi G, Virgili D, Bell Z R, Lazarides T, Calogero G, Armaroli N, Ward M D. Syntheses and crystal structures of dinuclear complexes containing d-block and f-block luminophores. Sensitization of NIR luminescence from Yb(III), Nd(III), and Er(III) centers by energy transfer from Re(I)and Pt(II)-bipyrimidine metal centers. Inorg Chem, 2005, 44: 61–72

    Article  CAS  Google Scholar 

  18. Lazarides T, Adams H, Sykes D, Faulkner S, Calogero G, Ward M D. Heteronuclear bipyrimidine-bridged Ru-Ln and Os-Ln dyads: low-energy 3MLCT states as energy-donors to Yb(III) and Nd(III). Dalton Trans, 2008: 691–698

  19. Shavaleev N M, Moorcraft L P, Pope S J A, Bell Z R, Faulkner S, Ward M D. Sensitized near-infrared emission from complexes of YbIII, NdIII and ErIII by energy-transfer from covalently attached PtII-based antenna units. Chem Eur J, 2003, 9: 5283–5291

    Article  CAS  Google Scholar 

  20. Kennedy F, Shavaleev N M, Koullourou T, Bell Z R, Jeffery J C, Faulkner S, Ward M D. Sensitised near-infrared luminescence from lanthanide(III) centres using Re(I) and Pt(II) diimine complexes as energy donors in d-f dinuclear complexes based on 2,3-bis(2-pyridyl) pyrazine. Dalton Trans, 2007: 1492–1499

  21. Rasmussen S C, Richter M M, Yi E, Place H, Brewer K J. Synthesis and characterization of a series of novel rhodium and iridium complexes containing polypyridyl bridging ligands — Potential uses in the development of multimetal catalysts for carbon-dioxide reduction. Inorg Chem, 1990, 29: 3926–3932

    Article  CAS  Google Scholar 

  22. Nallas G N A, Jones S W, Brewer K J. Bipyrimidine-bridged mixed-metal trimetallic complexes of ruthenium(II) with rhodium(III) or iridium(III), {[(bpy)2Ru(bpm)]2MCl2}5+. Inorg Chem, 1996, 35: 6974–6980

    Article  CAS  Google Scholar 

  23. Coppo P, Plummer E A, De Cola L. Tuning iridium(III) phenylpyridine complexes in the “almost blue” region. Chem Commun, 2004: 1774–1775

  24. Chen F F, Bian Z Q, Huang C H. Synthesis, crystal structure and photoluminescence properties of an organometallic Ir complex containing 2,2′-bipyrimidine as ancillary ligand. Chinese J Inorg Chem, 2008, 24: 1219–1223

    CAS  Google Scholar 

  25. Sager W F, Filipescu N, Serafin F A. Substituent effects on intramolecular energy transfer. I. Absorption and phosphorescence spectra of rare earth beta-diketone chelates. J Phys Chem, 1965, 69: 1092–1100

    Article  CAS  Google Scholar 

  26. Ronson T K, Lazarides T, Adams H, Pope S J A, Sykes D, Faulkner S, Coles S J, Hursthouse M B, Clegg W, Harrington R W, Ward M D. Luminescent PtII(bipyridyl)(diacetylide) chromophores with pendant binding sites as energy donors for sensitised near-infrared emission from lanthanides: Structures and photophysics of PtII/Ln(III) assemblies. Chem Eur J, 2006, 12: 9299–9313

    Article  CAS  Google Scholar 

  27. Benesi H A, Hildebrand J H. A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J Am Chem Soc, 1949, 71: 2703–2707

    Article  CAS  Google Scholar 

  28. Barra M, Bohne C, Scaiano J C. Effect of cyclodextrin complexation on the photochemistry of xanthone — Absolute measurement of the kinetics for triplet-state exit. J Am Chem Soc, 1990, 112: 8075–8079

    Article  CAS  Google Scholar 

  29. Fery-Forgues S, Le Bris M T, Guette J P, Valeur B. Ion-responsive fluorescent compounds. 1. Effect of cation binding on photophysical properties of a benzoxazinone derivative linked to monoaza-15-crown-5. J Phys Chem, 1988, 92: 6233–6237

    Article  CAS  Google Scholar 

  30. Dean A J, Lange’s Chemistry Handbook. 15th ed. New York: McGraw-Hill Book Company, 1999.

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    FangFang Chen, WeiLi Jiang, Bin Lou, ZuQiang Bian & ChunHui Huang

Authors
  1. FangFang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. WeiLi Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Bin Lou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. ZuQiang Bian
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. ChunHui Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to ChunHui Huang.

Additional information

Supported by the National Basic Research Program of China (Grant No. 2006CB601103) and the National Natural Science Foundation of China (Grant Nos. 20221101, 50772003, 20671006, 20971006, and 90922004)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chen, F., Jiang, W., Lou, B. et al. Synthesis and photophysical properties of IrIII-LnIII (Ln = Nd, Yb, Er) bimetallic complexes containing bipyrimidines as bridging ligands. Sci. China Ser. B-Chem. 52, 1808–1813 (2009). https://doi.org/10.1007/s11426-009-0269-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-009-0269-7

Keywords

Search

Navigation