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Study by fluorescence of calix[4]arenes bearing heterocycles with anions: highly selective detection of iodide

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Abstract

The present work describes a study of complexation efficiency of calix[4]arenes bearing benzoimidazolyl, benzothiazolyl, and benzoxazolyl heterocycles (5–7) towards several anions. The binding ability of calixarene derivatives 5–7 towards selected anions of different molecular geometries such as: F−, HSO4 −, I−, N3 −, NO3 −, NO2 −, SCN−, ClO4 −, Br−, CN−, Cl−, CH3COO− CF3SO3 − in methanol, has been investigated by fluorescence spectroscopic techniques, all anions were used as tetrabutylammonium salts to avoid possible complexation of cationic species by the derivative calix[4]arenes. Fluorescent chemosensor ability of these three calixarene derivatives was highly selective for iodide in contrast with other anions studied. The best chemosensor found, corresponds to compound 7, with an association constant of 2.01 × 104 mol−1 L and a detection limits of 0.22 ppm for iodide.

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References

  1. Beer, P., Gale, P.: Anion recognition and sensing: the state of the art and future perspectives. Angew. Chem. Int. Ed. Engl. 40, 486–516 (2001)

    Article  CAS  Google Scholar 

  2. Amendola, V., Bonizzoni, M., Esteban-Gomez, D., Fabbrizzi, L., Licchelli, M., Sancenon, F., Taglietti, A.: Some guidelines for the design of anion receptors. Coord. Chem. Rev. 250, 1451–1470 (2006)

    Article  CAS  Google Scholar 

  3. Kuswandi, B., Verboom, W., Reinhoudt, D.: Tripodal receptors for cation and anion sensors. Sensors 6, 978–1017 (2006)

    Article  CAS  Google Scholar 

  4. Prados, P., Quesada, R.: Recent advances in macrocyclic and macrocyclic-based anion receptors. Supramol. Chem. 20, 201–216 (2008)

    Article  CAS  Google Scholar 

  5. Kubik, S.: Amino acid containing anion receptors. Chem. Soc. Rev. 38, 585–605 (2009)

    Article  CAS  Google Scholar 

  6. Gale, P., Busschaert, N., Haynes, C., Karagiannidis, L., Kirby, I.: Anion receptor chemistry: highlights from 2011 and 2012. Chem. Soc. Rev. 43, 205–241 (2014)

    Article  CAS  Google Scholar 

  7. Asfari, Z., Böhmer, V., Harrowfield McB, M., Vicens, J.: Calixarenes. Kluwer Academic, Dordrecht (2001)

    Google Scholar 

  8. Mokhtari, B., Pourabdollah, K., Dalali, N.: Analytical applications of calixarenes from 2005 up-to-date. J. Incl. Phenom. Macrocycl. Chem. 69, 1–55 (2011)

    Article  CAS  Google Scholar 

  9. Kim, J.S., Quang, D.T.: Calixarene-derived fluorescent probes. Chem. Rev. 107, 3780–3799 (2007)

    Article  CAS  Google Scholar 

  10. Kim, J.S., Lee, S.Y., Yoon, J., Vicens, J.: Hyperbranched calixarenes: synthesis and applications as fluorescent probes. Chem. Commun. 32, 4791–4802 (2009)

    Article  Google Scholar 

  11. Stoddart, J.F. (ed.): Calixarenes Revisited. Royal Society of Chemistry, Cambridge (1998)

    Google Scholar 

  12. Gutsche, C.D., Iqbal, M.: p-tert-Butylcalix[4]arene. Org. Synth 8, 75–77 (1993)

    Google Scholar 

  13. Ludwig, R., Kim Dzung, N.T.: Calixarene-based molecules for cation recognition. Sensors 2, 397–416 (2002)

    Article  Google Scholar 

  14. Arora, V., Chawla, H.M., Singh, S.P.: Calixarene as sensor materials for recognition and separation of metal ions. Arkivoc (ii). 172–200 (2007)

  15. Sliwa, W., Girek, T.: Calixarene complexes with metal ions. J. Incl. Phenom. Macrocyclic. Chem. 66, 15–41 (2010)

    Article  CAS  Google Scholar 

  16. Joseph, R., Rao, C.P.: Ion and molecular recognition by lower rim 1,3-di-conjugates of calix[4]arene as receptors. Chem. Rev. 111(8), 4658–4702 (2011)

    Article  CAS  Google Scholar 

  17. Shokova, E.A., Kovalev, V.V.: Calixarene-based anionic receptors. Russ. J. Org. Chem. 45(9), 1275–1314 (2009)

    Article  CAS  Google Scholar 

  18. Matthews, S.E., Beer, P.D.: Calixarene-based anion receptors. Supramol. Chem. 17, 411–435 (2005)

    Article  CAS  Google Scholar 

  19. Lhoták, P.: Anion receptors based on calixarenes. Top. Curr. Chem. 255, 65–95 (2005)

    Google Scholar 

  20. Edwards, N.Y., Possanza, A.L.: Calixarene-based anionic receptors: highlights from 2011. Supramol. Chem. 25(7), 446–463 (2013)

    Article  CAS  Google Scholar 

  21. Rodriguez-Docampo, Z., Pascu, S.I., Kubik, S., Otto, S.: Noncovalent interactions within a synthetic receptor can reinforce guest binding. J. A. Chem. Soc. 128, 11206–11210 (2006)

    Article  CAS  Google Scholar 

  22. Kumari, N., Hasan, M.A., Ward, B.D., Mishra, L.: Reactivity of tetrabutylammonium iodide with a heteronuclear 6Copper(II)-4Na(I) complex: selective recognition of iodide ion. Ind. Eng. Chem. Res. 52, 15007–15014 (2013)

    Article  CAS  Google Scholar 

  23. Mendy, J.S., Saeed, M.A., Fronczek, F.R., Powell, D.R., Hossain Md, A.: Anion recognition and sensing by a new macrocyclic dinuclear copper(II) complex: a selective receptor for iodide. Inorg. Chem. 49, 7223–7225 (2010)

    Article  CAS  Google Scholar 

  24. Liu, S.-Y., Xu, K.-X., He, Y.-B., Qin, H.-J., Meng, L.-Z.: New neutral receptors for fluoride based on Calix[4]arene bearing thiourea and amide. Chinese J. Chem. 23, 321–325 (2005)

    Article  CAS  Google Scholar 

  25. López, M.V., Bermejo, M.R., Vasquéz, M.E., Taglietti, A., Zaragoza, G., Pedrido, R., Martínez-Calvo, M.: Sulfonamide-imines as selective fluorescent chemosensors for the fluoride anion. Org. Biomol. Chem. 8, 357–362 (2010)

    Article  Google Scholar 

  26. Sakai, R., Okade, S., Barasa, E., Kakuchi, R., Ziabka, M., Umeda, S., Tsuda, K., Satoh, T., Kakuchi, T.: Efficient colorimetric anion detection based on positive allosteric system of urea-functionalized poly(phenylacetylene) receptor. Macromolecules 43, 7406–7411 (2010)

    Article  CAS  Google Scholar 

  27. Bonizzoni, M., Fabbrizzi, L., Taglietti, A., Tiengo, F.: (Benzylidenamino)thioureas-chromogenic interactions with anions and N-H deprotonation. Eur. J. Org. Chem. 16, 3567–3574 (2006)

    Article  Google Scholar 

  28. Singh, N., Jang, D.O.: Benzimidazole-based tripodal receptor: highly selective fluorescent chemosensor for iodide in aqueous solution. Org. Lett. 9(10), 1991–1994 (2007)

    Article  CAS  Google Scholar 

  29. Ghosh, K., Saha, I.: A new benzimidazolium receptor for fluorescence sensing of iodide. Supramol. Chem. 22(5), 311–317 (2010)

    Article  CAS  Google Scholar 

  30. Ghosh, K., Kar, D.: Fluorometric recognition of both dihydrogen phosphate and iodide by a new flexible anthracene linked benzimidazolium-based receptor. Beilstein J. Org. Chem. 7, 254–264 (2011)

    Article  CAS  Google Scholar 

  31. Ma, B., Zeng, F., Zheng, F., Wu, S.: A fluorescent turn-on sensor for iodide based on a thymine–Hg(II)–thymine complex. Chem. Eur. J. 17, 14844–14850 (2011)

    Article  CAS  Google Scholar 

  32. Tayade, K., Gallucci, J., Sharma, H., Attarde, S., Patil, R., Singh, N., Kuwar, A.: Exploration of selective recognition of iodide with dipodal sensor: 2, 2′-[ethane-1,2-diylbis(iminoethane-1,1-diyl)]diphenol. Dalton Trans. 43, 3584–3588 (2014)

    Article  CAS  Google Scholar 

  33. Cheng, H.-S., Yan, H., Sun, Y.-L., Lu, C.-L., Huang, T.-Y., Chen, S.-J., Hu, C.-H., Wu, Y.-Y., Wu, A.-T.: A simple and highly selective receptor for iodide in aqueous solution. Analyst 137, 571–574 (2012)

    Article  CAS  Google Scholar 

  34. Lee, D.Y., Singh, N., Kim, M.J., Jang, D.O.: Chromogenic and fluorescent recognition of iodide with benzoimidazole-based tripodal receptor. Org. Lett. 13(12), 3024–3027 (2011)

    Article  CAS  Google Scholar 

  35. Suresh, V., Ahmed, N., Youn, I.S., Kim, K.S.: An imidazolium-based fluorescent cyclophane for the selective recognition of iodide. Chem. Asian J. 7, 658–663 (2012)

    Article  CAS  Google Scholar 

  36. Kim, J.S., Park, S.Y., Kim, S.H., Thuéry, P., Souane, R., Matthews, S.E., Vicens, J.: A pyrenyl-appended triazole-based calix[4]arene as a fluorescent sensor for iodide ion. Bull. Korean Chem. Soc. 31(3), 624–629 (2010)

    Article  CAS  Google Scholar 

  37. Joseph, R., Chinta, J.P., Rao, C.P.: Benzothiazole appended lower rim 1,3-diamido-derivative of calix[4]arene: synthesis, structure, receptor properties towards Cu2+, iodide recognition and computational modeling. Inorg. Chim. Acta 363, 2833–2839 (2010)

    Article  CAS  Google Scholar 

  38. Joseph, R., Gupta, A., Ali, A., Rao, C.P.: Fluorescence and absorption studies on the selective recognition of iodide by lower rim 1,3-bis(aminoethoxy)-p-t-butyl-calix[4]arene derivate. Indian J. Chem. 46A, 1095–1100 (2007)

    CAS  Google Scholar 

  39. Quiroga-Campano, C., Gómez-Machuca, H., Jullian, C., De la Fuente, J., Pessoa-Mahana, H., Saitz, C.: Study by fluorescence of calix[4]arenes bearing heterocycles with divalents metals: highly selective detection of Pb(II). J. Incl. Phenom. Macrocyclic. Chem. 79, 161–169 (2014)

    Article  CAS  Google Scholar 

  40. Zhang, W.C., Huang, Z.T.: Synthesis of 4-tert-Butylcalix[4]arenes bearing two schiff-base units at lower rim. Synthesis 1997, 1073–1076 (1997)

    Article  Google Scholar 

  41. Santoyo-Gonzalez, F.A., Torres-Pinedo, A., Saitz-Barría, C.: An efficient synthesis of bis(calix[4]arenes), bis(crown-ether) substituted calix[4]arenes, aza-crown calix[4]arenes and thiaza-crown calix[4]arenes. Eur. J. Org. Chem. 3587–3593 (2000)

  42. Saitz, C., De La Fuente, J., Jullian, C., Pessoa, H., Olea, C.: Synthesis of calix[4]arenes bearing benzothiazolyl, benzoxazolyl and benzoimidazolyl heterocycles. J. Chem. Res. (S) 6, 324–326 (2008)

    Article  Google Scholar 

  43. Job, P.: Formation and stability of inorganic complexes in solution. Ann. Chim. 9, 113–203 (1928)

    CAS  Google Scholar 

  44. Amendola, V., Boioocchi, M., Fabbrizzi, L., Fusco, N.: Putting the anion into the cage-fluoride. Inclusion in the smallest tris-imidazolium macrotricycle. Eur. J. Org. Chem. 32, 6434–6444 (2011)

    Article  Google Scholar 

  45. Vasquez, M., Vasquez, M., Fabrizzi, Taglietti, A., Pedrido, R.M., González Noya, A.M., Bermejo, M.R.: A colorimetric approach to anion sensing: a selective chemosensor of fluoride Ions, in which color is generated by anion-enhanced π delocalization. Angew. Chem. Int. Ed. 43, 1962–1965 (2004)

    Article  Google Scholar 

  46. Connors, K.A.: Binding Constant: The Measurement of Molecular Complex Stability. Wiley, New York (1987)

    Google Scholar 

  47. Qazi, M.A., Ocak, U., Ocak, M., Memon, S., Solangi, I.B.: Bifunctional calix[4]arene sensor for Pb(II) and Cr2O7 2− ions. J. Fluoresc. 23, 575–590 (2013)

    Article  CAS  Google Scholar 

  48. Lee, J.L., Kim, S.K., Jung, J.H., Kim, J.S.: Bifunctional fluorescent calix[4]arene chemosensor for both a cation and anion. J. Org. Chem. 70, 1643–1646 (2005)

    Article  Google Scholar 

  49. Chang, K.-C., Su, I.-H., Wang, Y.-Y., Chung, W.-S.: A bifunctional chromogenic calix[4]arene chemosensor for both cations and anions: a potential Ca2+ and F-switched INHIBIT logic gate with a YES logic function. Eur. J. Org. Chem. 4700–4704 (2010)

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Acknowledgments

We thank FONDECYT (Grant 1100906).

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Authors and Affiliations

  1. Departamento de Química Orgánica y Físicoquimica, Facultad de Ciencias Químicas y Farmaceúticas, Universidad de Chile, Sergio Livingstone 1007 (Ex Olivos) Independencia, Casilla 233, Santiago 1, Chile

    Horacio Gómez-Machuca, Cinthia Quiroga-Campano, Carolina Jullian, Julio De la Fuente, Hernán Pessoa-Mahana & Claudio Saitz

  2. Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Universidad Andres Bello, República 275, Santiago, Chile

    Carlos A. Escobar

  3. Departamento de Química Orgánica, Facultad de Ciencias, calle Severo Ochoa s/n, Universidad de Granada, 18071, Granada, Spain

    José A. Dobado

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  1. Horacio Gómez-Machuca
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  2. Cinthia Quiroga-Campano
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Correspondence to Claudio Saitz.

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Gómez-Machuca, H., Quiroga-Campano, C., Jullian, C. et al. Study by fluorescence of calix[4]arenes bearing heterocycles with anions: highly selective detection of iodide. J Incl Phenom Macrocycl Chem 80, 369–375 (2014). https://doi.org/10.1007/s10847-014-0418-2

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  • DOI: https://doi.org/10.1007/s10847-014-0418-2

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