Skip to main content
SpringerLink
Log in

A hetero-bimetallic(Cu–Ru) chromogenic and fluorogenic complex as receptor of soft metal ions

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

A hetero-bimetallic complex of type [Cu(bpy)(NCS)(μ-NCS)Ru(bpy)2Cl]·PF6 is synthesized and characterized using spectroscopic studies, elemental analyses and ESI-MS data. Owing to the presence of sulphur donor ligand in the complex, its affinity towards soft metal ions is monitored. It detects selectively Hg2+ and Ag+ ions over a number of environmentally relevant cations including Mn2+, Pb2+, Zn2+, Cd2+, Ni2+, Cu2+, and Co2+. The naked eye response is more pronounced for Hg2+ as compared to Ag+ ions. The detection limit for Hg2+ ions is 1.0 ppm while for Ag+ ions are 10 ppm. However, fluorescence response is exclusive to Ag+ ions. The complex shows a tenfold enhancement in the fluorescence intensity upon addition of Ag+ ions while no change in emission intensity is observed upon addition of other cations including Hg2+. Competitive binding experiments using fluorescence spectrometry reveal that the complex binds Ag+ selectively even in presence of tenfold excess of other cations exclusive of Hg2+ ions. The emission from the complex obtained by addition of Ag+ ions is quenched upon addition of Hg2+ ions, displaying fluorescence on–off behavior.

Graphical Abstract

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Nolan, E.M., Lippard, S.J.: Tools and tactics for the optical detection of mercuric ion. Chem. Rev. 108, 3443 (2008)

    Article  CAS  Google Scholar 

  2. EPA: Mercury update: impact of fish advisories. EPA fact sheet EPA-823-F-01-011. EPA, Office of Water, Washington D.C. (2001)

    Google Scholar 

  3. Boening, D.W.: Ecological effects, transport, and fate of mercury: a general review. Chemosphere 40, 1335 (2000)

    Article  CAS  Google Scholar 

  4. Harris, H.H., Pickering, I.J., George, G.N.: The chemical form of mercury in fish. Science 301, 1203 (2003)

    Article  CAS  Google Scholar 

  5. Yoon, S., Albers, A.E., Wong, A.P., Chang, C.J.: Screening mercury levels in fish with a selective fluorescent chemosensor. J. Am. Chem. Soc. 127, 16030 (2005)

    Article  CAS  Google Scholar 

  6. Leray, I., Valeur, B.: Calixarene-based fluorescent molecular sensors for toxic metals. Eur. J. Inorg. Chem. 24, 3525 (2009)

    Article  Google Scholar 

  7. Caballero, A., Martınez, R., Lloveras, V., Ratera, I., Vidal-Gancedo, J., Wurst, K., Tarraga, A., Molina, P., Veciana, J.: Highly selective chromogenic and redox or fluorescent sensors of Hg2+ in aqueous environment based on 1,4-disubstituted azines. J. Am. Chem. Soc. 127, 15666 (2005)

    Article  CAS  Google Scholar 

  8. Hennrich, G., Walther, W., Resch-Genger, U., Sonnenschein, H.: Cu(II)- and Hg(II)-induced modulation of the fluorescence behavior of a redox-active sensor molecule. Inorg. Chem. 40, 641 (2001)

    Article  CAS  Google Scholar 

  9. Shunmugam, R., Gabriel, G.J., Smith, C.E., Aamer, K.A., Tew, G.N.: A highly selective colorimetric aqueous sensor for mercury. Chem. Eur. J. 14, 3904 (2008)

    Article  CAS  Google Scholar 

  10. Yang, Y.K., Yook, K.J., Tae, J.: A rhodamine-based fluorescent and colorimetric chemodosimeter for the rapid detection of Hg2+ ions in aqueous media. J. Am. Chem. Soc. 127, 16760 (2005)

    Article  CAS  Google Scholar 

  11. Ou, S., Lin, Z., Duan, C., Zhang, H., Bai, Z.: A sugar-quinoline fluorescent chemosensor for selective detection of Hg2+ ion in natural water. Chem. Commun. 42, 4392 (2006)

    Article  Google Scholar 

  12. Voutsadaki, S., Tsikalas, G.K., Klontzas, E., Froudakis, G.E., Katerinopoulos, H.E.: A “turn-on” coumarin-based fluorescent sensor with high selectivity for mercury ions in aqueous media. Chem. Commun. 46, 3292 (2010)

    Article  CAS  Google Scholar 

  13. Valeur, B., Leray, I.: Design principles of fluorescent molecular sensors for cation recognition. Coord. Chem. Rev. 205, 3 (2000)

    Article  CAS  Google Scholar 

  14. Prodi, L., Bolletta, F., Montalti, M., Zaccheroni, N.: Luminescent chemosensors for transition metal ions. Coord. Chem. Rev. 205, 59 (2000)

    Article  CAS  Google Scholar 

  15. Deo, S., Godwin, H.A.: A selective, ratiometric fluorescent sensor for Pb2+. J. Am. Chem. Soc. 122, 174 (2000)

    Article  CAS  Google Scholar 

  16. Yang, R.-H., Chan, W.-H., Lee, A.W.M., Xia, P.-F., Zhang, H.-K., Li, K.: A ratiometric fluorescent sensor for Ag+ with high selectivity and sensitivity. J. Am. Chem. Soc. 125, 2884 (2003)

    Article  CAS  Google Scholar 

  17. Lin, Z.H., Ou, S.J., Duan, C.Y., Zhang, B.G., Bai, Z.P.: Naked-eye detection of fluoride ion in water: a remarkably selective easy-to-prepare test paper. Chem. Commun. 6, 624 (2006)

    Article  Google Scholar 

  18. Dixit, N., Mishra, L., Mustafi, S.M., Chary, K.V.R., Houjou, H.: Synthesis of a ruthenium(II) bipyridyl complex coordinated by a functionalized Schiff base ligand: characterization, spectroscopic and isothermal titration calorimetry measurements of M2+ binding and sensing (M2+=Ca2+, Mg2+). Spectrochim. Acta A 73, 29 (2009)

    Article  Google Scholar 

  19. Shi, Y., Toms, B.B., Dixit, N., Kumari, N., Mishra, L., Goodisman, J., Dabrowiak, J.C.: Cytotoxicity of Cu(II) and Zn(II) 2,2′-bipyridyl complexes: dependence of IC50 on recovery time. Chem. Res. Toxicol. 23, 1417 (2010)

    Article  CAS  Google Scholar 

  20. Kumari, N., Dixit, M., Roesky, H.W., Mishra, L.: Chemistry for sustainable development. In: Bhowon, M.G., Jhaumeer-Lauloo, S., Li, H., Wah, K., Ramasami, P. (eds.) Chapter 15, p. 231. Springer, New York (2012)

  21. Sakaguchi, U., Addison, A.W.: Spectroscopic and redox studies of some copper(II) complexes with biomimetic donor atoms: implications for protein copper centres. J. Chem. Soc. Dalton Trans. 4, 600 (1979)

    Article  Google Scholar 

  22. Caspar, J.V., Meyer, T.J.: Photochemistry of MLCT excited states. Effect of nonchromophoric ligand variations on photophysical properties in the series cis-Ru(bpy)2L22+. Inorg. Chem. 22, 2444 (1983)

    Article  CAS  Google Scholar 

  23. Wolfe, A., Shimer, G.H., Meehan, T.: Polycyclic aromatic hydrocarbons physically intercalate into duplex regions of denatured DNA. Biochemistry 26, 6392 (1987)

    Article  CAS  Google Scholar 

  24. Benesi, H.A., Hildebrand, J.H.: A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J. Am. Chem. Soc. 71, 2703 (1949)

    Article  CAS  Google Scholar 

  25. Marcus, Y.: Ionic radii in aqueous solutions. Chem. Rev. 88, 1475 (1988)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  27. Misra, A., Shahid, M.: Chromo and fluorogenic properties of some azo-phenol derivatives and recognition of Hg2+ ion in aqueous medium by enhanced fluorescence. J. Phys. Chem. C 114, 16726 (2010)

    Google Scholar 

Download references

Acknowledgments

Financial support from DAE-BRNS (Grant No. 2005/37/33/BRNS/1807 to L. M.), Mumbai is gratefully acknowledged.

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, 221 005, India

    Namrata Dixit, Mohammad Shahid, Arvind Misra & Lallan Mishra

Authors
  1. Namrata Dixit
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mohammad Shahid
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Arvind Misra
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lallan Mishra
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Arvind Misra or Lallan Mishra.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Dixit, N., Shahid, M., Misra, A. et al. A hetero-bimetallic(Cu–Ru) chromogenic and fluorogenic complex as receptor of soft metal ions. J Incl Phenom Macrocycl Chem 76, 125–132 (2013). https://doi.org/10.1007/s10847-012-0181-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-012-0181-1

Keywords

Search

Navigation