Skip to main content
SpringerLink
Log in

Electrochemically controlled multistability of ultrathin films of double-decker cerium phthalocyaninates

  • Published:
Russian Journal of Electrochemistry Aims and scope Submit manuscript

Abstract

The spectral and electrochemical properties of Langmuir-Blodgett (LB) films of homoleptic double-decker cerium bis-[tetra-15-crown-5]-phthalocyaninate Ce[R4Pc]2 and its heteroleptic analog [Pc]Ce[R4Pc] were studied. It was shown that during formation of Langmuir monolayers upon contact of both complexes solutions with water subphase the metal center with valent state IV in the solution transforms into one with the valent state III in the monolayer. Upon cyclic compression-expansion of these monolayers, orientation-induced reversible intramolecular transfers of electron from 4f orbital of cerium ion to the phthalocyanine macrocycle (compression) and in reverse direction (expansion) occur in a planar supramolecular system. Scheme of reversible electrochemical transformations occurring in ultrathin films of double-decker cerium crown-phthalocyaninates, one of which is associated with the Ce+3/Ce+4 redox-transition of metal center of the complex, was proposed and substantiated using the results of spectro-electrochemical investigations. It was shown that one of these transformations is associated with the Ce+3/Ce+4 redox transition of metal center of the complex and upon change of metal center oxidation state its size changes, and, consequently, the distance between the decks of the complex also changes. This change in the distance can lead to a substantial (13–15%) modulation of the linear size of molecular assemblies with a large number of molecules in stack. On the basis of this effect the supramolecular device that can perform mechanical work can be developed. Using surface plasmon resonance technique we have demonstrated that a step change in electrode potential in region of 200–1000 mV induces a corresponding optical response reflected in a step change of the resonance angle. High operation speed and reversibility of switching between stable states can serve as a basis for development of optoelectronic switching systems.

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. Moskalev, P.N., Russ. J. Coord. Chem., 1990, vol. 16, no. 2, p. 147.

    CAS  Google Scholar 

  2. Tsivadze, A.Yu., Usp. Khim., 2004, vol. 73, p. 6.

    Google Scholar 

  3. Li, J., Gryko, D., Dabke, R.B., Diers, J.R., Bocian, D.F., Kuhr, W.G., and Lindsey, J.S.J., J. Org. Chem., 2000, vol. 65, p. 7379.

    Article  CAS  Google Scholar 

  4. Gryko, D., Li, J., Diers, J. R., Roth, K.M., Bocian, D. F., Kuhr, W.G., and Lindsey, J.S.J., J. Mater. Chem., 2001, vol. 11, p. 1162.

    Article  CAS  Google Scholar 

  5. Kobayashi, N., Coord. Chem. Rev., 2002, vol. 227, p. 129.

    Article  CAS  Google Scholar 

  6. Jiang, J. and Ng, D.K.P., Acc. Chem. Res., 2009, vol. 42, p. 79.

    Article  CAS  Google Scholar 

  7. Gao, Y., Ma, P., Chen, Y., Zhang, Y., Bian, Y., Li, X., Jiang, J., and Ma, C., Inorg. Chem., 2009, vol. 48, p. 45.

    Article  CAS  Google Scholar 

  8. Selector, S.L., Arslanov, V.V., Gorbunova, Y.G., Raitman, O.A., Sheinina, L.S., Birin, K.P., and Tsivadze, A.Yu., J. Porphyrins Phthalocyanines, 2008, vol. 12, p. 1154.

    Article  CAS  Google Scholar 

  9. Selektor, S.L., Raitman, O.A., Sheinina, L.S., Shokurov, A.V., Arslanov, V.V., Lapkina, L.A., Gorbunova, Yu.G., and Tsivadze, A.Yu., Prot. Met. Phys. Chem. Surf., 2011, vol. 47, no. 4, p. 447.

    Article  CAS  Google Scholar 

  10. Selektor, S.L., Shokurov, A.V., Raitman, O.A., Sheinina, L.S., Arslanov, V.V., Birin, K.P., Gorbunova, Yu.G., and Tsivadze, A.Yu., Colloid J., 2012 (in press).

  11. Rodriguez-Mendez, M. L., de Saja, J. A., J. Porphyrins Phthalocyanines, 2009, vol. 13., no. 4–5, p. 606.

    Article  Google Scholar 

  12. Pakhomov, L.G. and Leonov, E.S., Plenochnye struktury na osnove organicheskikh poluprovodnikov (Film Structures on the Basis of the Organic Semiconductors), Novgorod: Izd-vo NGU im. N.I. Lobachevskogo, 2007.

    Google Scholar 

  13. Grishina, A.D., Gorbunova, Yu.G., Zolotarevsky, V.I., Pereshivko, L.Ya., Enakieva, Yu.Yu., Krivenko, T.V., Savelyev, V., Vannikov, A.V., and Tsivadze, A.Yu., J. Porphyrins Phthalocyanines, 2009, vol. 13, no. 1, p. 92.

    Article  CAS  Google Scholar 

  14. Vannikov, A.V., Grishina, A.D., Gorbunova, Yu.G., Enakieva, Yu.Yu., Krivenko, T.V., Savel’ev, V.V., and Tsivadze, A.Yu., Zh. Fiz. Khim., 2006, vol. 80, no. 3, p. 537.

    Google Scholar 

  15. Leznoff, C.C. and Lever, A.B.P., Phthalocyanines. Properties and Application, 1-4 vols., New York: VCH Publ. Inc, 1989.

    Google Scholar 

  16. Kadish, K.M., Smith, K.M., and Guilard, R., The Porphyrin Handbook, 20 vols., San Diego: Academic Press, 2000.

    Google Scholar 

  17. Jiang, X.-J., Lo, P.-C., Tsang, Y.-M., Yeung, S.-L., Fong, W.-P., and Ng, D.K., Chem.-Eur. J., 2010, vol. 16, p. 4777.

    CAS  Google Scholar 

  18. Jiang, J., Kasuga, K., and Arnold, D.P., Supramolecular Photo-Sensitive and Electro-Active, New York: Materials. Acad. Press, 2001, p. 113.

    Google Scholar 

  19. Tomilova, L.G., Chernykh, E.V., Nikolaeva, T.B., Zelentsov, E.E., and Luk’yanets, E.A., Russ. J. Gen. Chem., 1984, no. 7, p. 1678.

  20. Bian, Y., Jiang, J., Tao, Y., Choi, M.T.M., Li, R., Ng, A.C.H., Zhu, P., Pan, N., Sun, X., Arnold, D.P., Zhou, Z.-Y., Li, H.-W., Mak, T.C.W., and Ng, D.K.P., J. Am. Chem. Soc., 2003, no. 125, p. 12257.

  21. Haghighi, M.S. and Homborg, H., Z. Naturforsch., B: J. Chem. Sci., 1991, vol. 46, p. 1641.

    CAS  Google Scholar 

  22. Ostendorp, G., Rotter, H.W., and Homborg, H., Z. Naturforsch., B: J. Chem. Sci., 1996, vol. 51, p. 567.

    CAS  Google Scholar 

  23. Huckstadt, H., Tuta, A., Goldner, M., Cornelissen, U., and Homborg, H., Z. Anorg. Allg. Chem., 2001, vol. 627, p. 485.

    Article  CAS  Google Scholar 

  24. Jiang, J., Liu, W., Poon, K.-W., Du, D., Arnold, D.P., and Ng, D.K.P., Eur. J. Inorg. Chem., 2000, p. 205.

  25. Gorbunova, Yu.G., Lapkina, L.A., and Tsivadze, A.Yu., J. Coord. Chem., 2003, vol. 56, no. 14, p. 1223.

    Article  CAS  Google Scholar 

  26. Gorbunova, Yu.G., Lapkina, L.A., Martynov, A.G., Biryukova, I.V., and Tsivadze, A. Yu., Koord. Khim, 2004, vol. 30, p. 263.

    Google Scholar 

  27. Martynov, A.G., Biryukova, I.V., Gorbunova, Yu.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2004, vol. 49, no. 3, p. 407.

    CAS  Google Scholar 

  28. Lapkina, L.A., Gorbunova, Yu.G., Larchenko, V.E., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2003, vol. 48, no. 7, p. 1164.

    CAS  Google Scholar 

  29. Ahsen, V. and Simon, J., J. Am. Chem. Soc., 1994, vol. 116, p. 5352.

    Article  Google Scholar 

  30. Gorbunova, Yu.G. and Tsivadze, A.Yu., in Sovremennye problemy obshchei i neorganicheskoi khimii (Modern Problems of General and Inorganic Chemistry), Moscow, 2009, p. 238.

  31. Lapkina, L.A., Sakharov, S.G., Larchenko, V.E., Gorbunova, Yu.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2007, vol. 52, no. 4, p. 601.

    Article  CAS  Google Scholar 

  32. Tolkaeva, E.O., Tsivadze, A.Yu., Bitiev, Sh.G., Gorbunova, Yu.G., Zhilov, V.I., and Minin, V.V., Zh. Neorg. Khim., 1995, vol. 40, p. 984.

    Google Scholar 

  33. Birin, K.P., Gorbunova, Yu.G., and Tsivadze, A.Yu., J. Porphyrins Phthalocyanines, 2006, vol. 10, no. 7, p. 931.

    Article  CAS  Google Scholar 

  34. Birin, K.P., Gorbunova, Yu.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2007, vol. 52, no. 2, p. 232.

    Article  CAS  Google Scholar 

  35. Nefedova, I.V., Gorbunova, Yu.G., Sakharov, S.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2005, vol. 50, no. 2, p. 204.

    CAS  Google Scholar 

  36. Grüniger, H., Möbius, D., and Meyer, H., J. Chem. Phys., 1983, vol. 79, no. 8, p. 3701.

    Article  Google Scholar 

  37. Orrit, M., Möbius, D., Meyer, H., and Lehmann, U., J. Chem. Phys., 1986, vol. 85, no. 9, p. 4966.

    Article  CAS  Google Scholar 

  38. Martynov, A.G. and Gorbunova, Yu.G., Inorg. Chim. Acta, 2007, vol. 360, no. 1, p. 122.

    Article  CAS  Google Scholar 

  39. Martynov, A.G., Zubareva, O.V., Gorbunova, Yu.G., Sakharov, S.G., Nefedov, S.E., Dolgushin, F.M., and Tsivadze, A.Yu., Eur. J. Inorg. Chem, 2007, no. 30, p. 4800.

  40. Martynov, A.G., Zubareva, O.V., Gorbunova, Yu.G., Sakharov, S.G., and Tsivadze, A.Yu., Inorg. Chim. Acta, 2009, vol. 362, no. 11, p. 11.

    Article  CAS  Google Scholar 

  41. Martynov, A.G., Safonova, E.A., Gorbunova, Yu.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2010, vol. 55, no. 3, p. 389.

    Article  Google Scholar 

  42. Aroca, R. and Johnson, E., Langmuir, 1992, vol. 8, p. 3137.

    Article  CAS  Google Scholar 

  43. Tomilova, L.G., Ovchinnikova, N.A., and Luk’yanets, E.A., Russ. J. Gen. Chem., 1992, vol. 62, no. 7, p. 1631.

    Google Scholar 

  44. Nefedov, V.I., Gati, D., Dzhurinskii, B.F., Sergushin, N.P., and Salyn, Y.V., Russ. J. Inorg. Chem., 1975, vol. 20, p. 2307.

    CAS  Google Scholar 

  45. Dauscher, A., Hilaire, L., LeNormand, F., Muller, W., Maire, G., and Vasquez, A., Surf. Interface Anal., 1990, vol. 16, p. 341.

    Article  CAS  Google Scholar 

  46. Ingo, G.M., Paparazzo, E., Bagnarelli, O., and Zacchetti, N., Surf. Interface Anal., 990, vol. 16, p. 515.

  47. Barr, T.L., Fries, C.G., Cariati, F., Bart, J.C.J., and Giordano, N., J. Chem. Soc., Dalton Trans., 1983, vol. 9, p. 1825.

    Article  Google Scholar 

  48. Praline, G., Koel, B.E., Hance, R.L., Lee, H.I., and White, J.M., J. Electron Spectrosc. Relat. Phenom., 1980, vol. 21, p. 17.

    Article  CAS  Google Scholar 

  49. Schlapbach, L. and Osterwalder, J., Solid State Commun., 1982, vol. 42, p. 271.

    Article  CAS  Google Scholar 

  50. Schlapbach, L., Osterwalder, J., and Siegmann, H.C., J. Less-Common Met., 1982, vol. 88, p. 291.

    Article  CAS  Google Scholar 

  51. Ishikawa, N., Okubo, T., and Kaizu, Y., Inorg. Chem., 1999, vol. 38, p. 3173.

    Article  CAS  Google Scholar 

  52. Magdesyeva, T.V., Zhukov, I.V., Tomilova, L.G., Chernych, E.V., and Butin, K.P., Russ. Chem. Bull., 1997, vol. 46, p. 2036.

    Article  Google Scholar 

  53. Rodriguez-Mendez, M. L., Souto, J., de Saja-Gonzalez, J., and de Saja, J.A., Sens. Actuators, 1996, vol. 31, p. 51.

    Article  Google Scholar 

  54. Gorbunova, Yu.G., Rodriquez-Mendez, M.L., Kalashnikova, I.P., Tomilova, L.G., and de Saja, J.A., Langmuir, 2001, vol. 17, p. 5004.

    Article  CAS  Google Scholar 

  55. Bardin, M., Bertounesque, E., Plichon, V., et al., J. Electroanal. Chem., 1989, vol. 271, no. 1–2, p. 173.

    Article  CAS  Google Scholar 

  56. Rodriguez-Mendez, M.L., Aroca, R., and DeSaja, J.A., Chem. Mater., 1993, vol. 5, p. 933.

    Article  CAS  Google Scholar 

  57. Tomilova, L.G., Chernykh, E.V., Luk’yanets, E.A., and Ioffe, N.T., Russ. J. Gen. Chem., 1983, vol. 53, no. 11, p. 2594.

    CAS  Google Scholar 

  58. Revina, A.A., Volod’ko, V.V., and Radyushkina, K.A., Kinet. Katal., 1990, vol. 31, no. 6, p. 1321.

    CAS  Google Scholar 

  59. Martynov, A.G., Biryukova, I.V., Gorbunova, Yu.G., and Tsivadze, A.Yu., Russ. J. Inorg. Chem., 2004, vol. 49, no. 3, p. 407.

    CAS  Google Scholar 

  60. Raitman, O.A., Katz, E., Willner, I., Chegel, V.I., and Popova, G.V., Angew. Chem., Int. Ed. Engl., 2001, vol. 40, no. 19, p. 3649.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow, Leninsky pr. 31, 119071, Russia

    S. L. Selector, A. V. Shokurov, V. V. Arslanov, Yu. G. Gorbunova, O. A. Raitman, A. A. Isakova, K. P. Birin & A. Yu. Tsivadze

Authors
  1. S. L. Selector
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. V. Shokurov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. V. Arslanov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yu. G. Gorbunova
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. O. A. Raitman
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. A. Isakova
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. K. P. Birin
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. A. Yu. Tsivadze
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. L. Selector.

Additional information

Original Russian Text © S.L. Selector, A.V. Shokurov, V.V. Arslanov, Yu.G. Gorbunova, O.A. Raitman, A.A. Isakova, K.P. Birin, A.Yu. Tsivadze, 2012, published in Elektrokhimiya, 2012, Vol. 48, No. 2, pp. 240–256.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Selector, S.L., Shokurov, A.V., Arslanov, V.V. et al. Electrochemically controlled multistability of ultrathin films of double-decker cerium phthalocyaninates. Russ J Electrochem 48, 218–233 (2012). https://doi.org/10.1134/S1023193512020164

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1023193512020164

Keywords

Search

Navigation