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Electrochemical properties of outer-sphere associates of bipyridyl and sepulchrate metal complexes with (thia)calix[4]arenes

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Abstract

The electrochemical one-electron reduction (oxidation) of bipyridyl metal complexes ([Co(bipy)3]3+, [Cr(bipy)3]3+, [Fe(bipy)3]2+, [Ru(bipy)3]2+ (as well as Co(III) sepulcrate)) with water-soluble (thia)calix[4]arenes has been studied by means of cyclic voltammetry. It has been shown that [M(bipy)3]3+/2+ bind to (thia)calix[4]arenes via sulfonate groups of the upper rim. Oxidized forms bind stronger than reduced ones leading to reduction (oxidation) of half-wave cathodic shift. The effect of predominant stabilization of oxidized forms of metal complexes for carboxylated calix[4]arene is stronger than for thiacalix[4]arene (ΔΔG0 = − 7.8 ÷ − 12.5 and − 3.7 kJ/mol, respectively). The redox-switchable outer-sphere binding of Co(III) sepulchrate via lower rim of carboxylated calix[4]arene has been revealed using cyclic voltammetry. The binding constants of outer-sphere associates based on calix[4]arenes and unstable metal complexes ([Co(sep)]2+, [Ru(bipy)3]3+, [Co(bipy)3]2+) have been calculated for the first time using 1H NMR titration and cyclic voltammetry data.

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References

  1. T. Horiuchi, J. Shiori, T. Hirao, Redox-switchable conjugated bimetallic ruthenium(II) complexes. Tetrahedron Lett. 48, 5970–5972 (2007)

    Article  CAS  Google Scholar 

  2. V. Leeuven, T.C. Pijper, J. Areephong, B.L. Feringa, W.R. Browne, N. Katsonis, Reversible photochemical control of cholesteric liquid crystals with a diamine-based diarylethene chiroptical switch. J. Mat. Chem. 21, 3142–3146 (2011)

    Article  CAS  Google Scholar 

  3. Y. Yildiz, S. Impellizzeri, E. Deniz, D. McCaughan, J.F. Callan, F.-I.M. Raymo, Supramolecular strategies to construct biocompatible and photoswitchable fluorescent assemblies. J. Am. Chem. Soc. 133, 871–879 (2011)

    Article  CAS  PubMed  Google Scholar 

  4. L.M. Moretto, T. Kohls, A. Chovin, N. Sojic, P. Ugo, Epifluorescence imaging of electrochemically switchable Langmuir–Blodgett films of nafion. Langmuir 24, 6367–6374 (2008)

    Article  CAS  PubMed  Google Scholar 

  5. J.M. Spruell, W.F. Paxton, J.-C. Olson, D. Benitez, E. Tkatchouk, C.L. Stern, A. Trabolsi, D.C. Friedman, W.A. Goddart, J.F. Stoddart, A push-button molecular switch. J. Am. Chem. Soc. 11, 11571–11580 (2009)

    Article  CAS  Google Scholar 

  6. D. Canevet, M. Salle, G. Zhang, D. Zhu, Tetrathiafulvalene (TTF) derivatives: Key building-blocks for switchable processes. Chem. Commun. 17, 2245–2269 (2009)

    Article  CAS  Google Scholar 

  7. K.C.-F. Leung, C.-P. Chak, C.-M. Lo, W.-Y. Wong, S. Xuan, C.H.K. Cheng, pH-controllable supramolecular systems. Chem. Asian. J. 4, 364–381 (2009)

    Article  CAS  PubMed  Google Scholar 

  8. P.G.A. Janssen, A. Ruiz-Carretero, D. Gonzales-Rodriguez, E.W. Meijer, A.P. Schenning pH-switchable helicity of DNA-templated assemblies. Angew. Chem. Int. Ed. 48, 8103–8106 (2009)

    Article  CAS  Google Scholar 

  9. A.E. Kaifer, Supramolecular electrochemistry, (Wiley-VCH, Weinheim, 1999), p. 256

    Book  Google Scholar 

  10. P.L. Boulas, M. Gomez-Kaifer, L. Echegoyen, Electochemistry of supramolecular systems. Angew. Chem. Int. Ed. 37, 216–247 (1998)

    Article  CAS  Google Scholar 

  11. Y.-L. Zhao, W.R. Dichtel, A. Trabolsi, S. Saha, I. Aprahamian, J.F. Stoddart, A redox-switchable α-cyclodextrin-based [2]rotaxane. J. Am. Chem. Soc. 130, 11294–11296 (2008)

    Article  CAS  PubMed  Google Scholar 

  12. S. Dolder, S.-X. Liu, F. Le Derf, M. Salle, A. Neels, S. Decurtins, An original redox-responsive ligand based on a π-extended TTF framework. Org. Lett. 9, 3753–3756 (2007)

    Article  CAS  PubMed  Google Scholar 

  13. P.D. Beer, P.A. Gale, Anion recognition and sensing: the state of the art and future perspectives. Angew. Chem. Int. Ed. 40, 486–515 (2001)

    Article  CAS  Google Scholar 

  14. A. Stepanov, Elektrochemicheskij electronnij perenos i inducirovannie im processi v sistemah na osnove n-sulfinatnih (tia)calix[4]arenov i ionov (komplexov) metallov (Electrochemical electron transfer and induced processes in systems based on p-sulfonated (thia)calix[4]arenes and metal ions (complexes), PhD thesis, Kazan, 2011, pp. 1-149

  15. T. Matsue, T. Kato, U. Akiba, T. Osa, Electron-transfer reactions associated with host-guest complexation. Oxidation of ferrocenecarboxylic acid in the presence of β-cyclodextrin. J. Am. Chem. Soc. 107, 3411–3417 (1985)

    Article  CAS  Google Scholar 

  16. A. Paillert, G. Herzog, D.W.M. Arrigan, Electrochemical activity of phenolic calixarenes. Electrochem. Commun. 5, 68–72 (2003)

    Article  Google Scholar 

  17. P.L. Boulas, M. Gomez-Kaifer, L. Echegoyen, Electrochemistry of supramolecular systems. Angew. Chem. Int. Ed. 37, 216–247 (1998)

    Article  CAS  Google Scholar 

  18. A. Niemz, V.M. Rotello, From enzyme to molecular device. Exploring the interdependence of redox and molecular recognition. Acc. Chem. Res. 32, 44–52 (1999)

    Article  CAS  Google Scholar 

  19. P.D. Beer, P.A. Gale, G.Z. Chen, Electrochemical molecular recognition: pathways between complexation and signaling. J. Chem. Soc. Dalton Trans. 12, 1897–1909 (1987)

    Google Scholar 

  20. J. Alvares, Y. Wang, M. Gomez-Kaifer, A.E. Kaifer, Importance of intramolecular hydrogen bonding for preorganization and binding of molecular guests by water-soluble calix[6]arene hosts. Chem. Commun. 14, 1455–1456 (1988)

    Google Scholar 

  21. V. Burilov, Geterometallicheskiye komplexi i redox-perekluchaemie ystroistva na osnove proizvodnih sylfonatnih calix[4]arenov (Heterometallic complexes and redox-switchable devices based on derivatives of sulfonated calix[4]arenes, PhD thesis, Kazan, 2010, pp. 1–123

  22. M. Wu, F. Jiang, M. Hong, Inclusion of p-Sulfonatothiacalix[4]arene and Its metal complexes. Chem. Rec. 9, 155–168 (2009)

    Article  CAS  PubMed  Google Scholar 

  23. N. Iki, T. Horiuchi, H. Oka, K. Koyama, N. Morohashi, C. Kabuto, S. Miano, Energy transfer luminescence of Tb3 + ion complexed with calix[4]arenetetrasulfonate and the thia and sulfonyl analogue. The effect of bridging groups. J. Chem. Soc. Perkin Trans. 2, 2219–2225 (2001)

    Article  CAS  Google Scholar 

  24. Y. Wang, S. Mendoza, A.E. Kaifer, Electrochemical reduction of cobaltocenium in the presence of β-cyclodextrin. Inorg. Chem. 37, 317–320 (1998)

    Article  CAS  Google Scholar 

  25. C.M. Cardona, A.E. Kaifer, Asymmetric redox-active dendrimers containing a ferrocene subunit. Preparation, characterization, and electrochemistry. J. Am. Chem. Soc. 120, 4023–4024 (1998)

    Article  CAS  Google Scholar 

  26. J. Ferguson, C.J. Hawkins, L.A.P. Kane-Maguire, H. Lip, Absolute configurations of 1,10-phenantroline and 2,2-bipyridine metal complexes. Inorg. Chem. 8, 771–780 (1969)

    Article  CAS  Google Scholar 

  27. F.H. Brustall, R.S. Nyholm, Magnetic moments and bond types of transition-metal complexes. Studies in co-ordination chemistry. Part XIII, 3570–3579 (1952)

  28. N. Iki, T. Fujimoto, S. Miyano, A new water-soluble host molecule derived from thiacalixarene. Chem. Lett. 27, 625–626 (1998)

    Article  Google Scholar 

  29. A. Casnati, Y. Ting, D. Berti, M. Fabbi, A. Pochini, R. Ungaro, D. Sciotto, G.G. Lombardo, Synthesis of water soluble molecular receptors from calix[4]arenes fixed in the cone conformation. Tetrahedron 49, 9815–9822 (1993)

    Article  CAS  Google Scholar 

  30. E. Merck, Methodes d’Analyses Complexometriques par les Titriplex. (Darmstadt 1964)

  31. Z. Galus, Teoretyczne podstawy elektroanalizy chemicznej (Warszawa, 1971), pp. 1–552

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Authors and Affiliations

  1. Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov str., 8, 420088, Kazan, Russia

    Alexey Stepanov, Vitaly Yanilkin, Asiya Mustafina & Svetlana Solovieva

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  1. Alexey Stepanov
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  2. Vitaly Yanilkin
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  4. Svetlana Solovieva
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Correspondence to Alexey Stepanov.

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Stepanov, A., Yanilkin, V., Mustafina, A. et al. Electrochemical properties of outer-sphere associates of bipyridyl and sepulchrate metal complexes with (thia)calix[4]arenes. J IRAN CHEM SOC 15, 2251–2258 (2018). https://doi.org/10.1007/s13738-018-1414-z

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