Russian Chemical Bulletin

, Volume 67, Issue 12, pp 2195–2200 | Cite as

Spectrophotometric study of the cation-induced dimerization of heteroleptic terbium(III) tetra-15-crown-5-bisphthalocyaninate

  • A. G. MartynovEmail author
  • A. V. Bykov
  • Yu. G. Gorbunova
  • A. Yu. Tsivadze
Full Articles


We proposed a new approach to the synthesis of heteroleptic crown-substituted terbium(III) bisphthalocyaninate, [(15C5)4Pc]Tb(Pc) (1) based on the reaction of unsubstituted lanthanum bisphthalocyaninate (La(Pc)2) with tetra-15-crown-5-phthalocyanine (H2[(15C5)4Pc]) and terbium(III) acetate in a mixture of octanol and chloronaphthalene in the presence of 1,8-diazabicyclo[ 5.4.0]undec-7-ene as an organic base. For the first time, we carried out a comparative spectrophotometric titration of compound 1 with MBPh4 solutions (M = K, Rb, Cs) and demonstrated the formation of isostructural cofacial supramolecular dimers. Spectral-structural correlations were developed for evaluation of the distances between phthalocyanine ligands in new supramolecular assemblies, which can be used for the development of polynuclear suprasingle-molecule magnetic materials.

Key words

spectrophotometry terbium(III) tetra-15-crown-5-bisphthalocyaninate supramolecular assembly 


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  1. 1.
    J. L. Zhang, J. Q. Zhong, J. D. Lin, W. P. Hu, K. Wu, G. Q. Xu, A. T. S. Wee, W. Chen, Chem. Soc. Rev., 2015, 44, 2998–3022.CrossRefGoogle Scholar
  2. 2.
    C. Cheng, J. F. Stoddart, ChemPhysChem, 2016, 1780–1793.Google Scholar
  3. 3.
    M. Hagiya, A. Konagaya, S. Kobayashi, H. Saito, S. Murata, Acc. Chem. Res., 2014, 47, 1681–1690.CrossRefGoogle Scholar
  4. 4.
    A. K. Bar, C. Pichon, J.-P. Sutter, Coord. Chem. Rev., 2016, 308, 346–380.CrossRefGoogle Scholar
  5. 5.
    L. K. Thompson, L. N. Dawe, Coord. Chem. Rev., 2015, 289–290, 13–31.CrossRefGoogle Scholar
  6. 6.
    H. Wang, B. W. Wang, Y. Bian, S. Gao, J. Jiang, Coord. Chem. Rev., 2016, 306, 195–216.CrossRefGoogle Scholar
  7. 7.
    H. L. C. Feltham, S. Brooker, Coord. Chem. Rev., 2014, 276, 1–33.CrossRefGoogle Scholar
  8. 8.
    S. Gómez-Coca, D. Aravena, R. Morales, E. Ruiz, Coord. Chem. Rev., 2015, 289–290, 379–392.CrossRefGoogle Scholar
  9. 9.
    D. N. H. Roberta Sessoli, Hui Lien Tsai, A. R. Schake, Sheyi Wang, J. B. Vincent, K. Folting, D. Gatteschi, G. Christou, J. Am. Chem. Soc., 1993, 115, 1804–1816.CrossRefGoogle Scholar
  10. 10.
    A. J. Tasiopoulos, A. Vinslava, W. Wernsdorfer, K. A. Abboud, G. Christou, Angew. Chem., Int. Ed., 2004, 43, 2117–2121.CrossRefGoogle Scholar
  11. 11.
    C. J. Milios, A. Vinslava, W. Wernsdorfer, S. Moggach, S. Parsons, S. P. Perlepes, G. Christou, E. K. Brechin, J. Am. Chem. Soc., 2007, 129, 2754–2755.CrossRefGoogle Scholar
  12. 12.
    N. Ishikawa, M. Sugita, T. Ishikawa, S.-Y. Koshihara, Y. Kaizu, J. Am. Chem. Soc., 2003, 125, 8694–5.CrossRefGoogle Scholar
  13. 13.
    S. T. Liddle, J. Van Slageren, Chem. Soc. Rev., 2015, 44, 6655–6669.CrossRefGoogle Scholar
  14. 14.
    N. Ishikawa, S. Otsuka, Y. Kaizu, Angew. Chem., Int. Ed. Engl., 2005, 44, 731–3.CrossRefGoogle Scholar
  15. 15.
    Y. Horii, S. Kishiue, M. Damjanovic, K. Katoh, B. K. Breedlove, M. Enders, M. Yamashita, Chem. Eur. J., 2018, 4320–4327.Google Scholar
  16. 16.
    M. Kasha, H. R. Rawls, M. A. El-Bayoumi, Pure Appl. Chem., 1965, 11, 371–392.CrossRefGoogle Scholar
  17. 17.
    N. Kobayashi, A. B. P. Lever, J. Am. Chem. Soc., 1987, 109, 7433–7441.CrossRefGoogle Scholar
  18. 18.
    A. G. Martynov, Y. G. Gorbunova, Inorg. Chim. Acta, 2007, 360, 122–130.CrossRefGoogle Scholar
  19. 19.
    Y. G. Gorbunova, A. D. Grishina, A. G. Martynov, T. V. Krivenko, A. A. Isakova, V. V. Savel’ev, S. E. Nefedov, E. V. Abkhalimov, A. V. Vannikov, A. Y. Tsivadze, J. Mater. Chem. C, 2015, 3, 6692–6700.CrossRefGoogle Scholar
  20. 20.
    A. G. Martynov, O. V. Zubareva, Y. G. Gorbunova, S. G. Sakharov, S. E. Nefedov, F. M. Dolgushin, A. Y. Tsivadze, Eur. J. Inorg. Chem., 2007, 4800–4807.Google Scholar
  21. 21.
    A. Yu. Tsivadze, A. G. Martynov, M. A. Polovkova, Yu. G. Gorbunova, Russ. Chem. Bull., 2011, 60, 2258–2262.CrossRefGoogle Scholar
  22. 22.
    R. J. Holmberg, M. A. Polovkova, A. G. Martynov, Y. G. Gorbunova, M. Murugesu, Dalton Trans., 2016, 45, 9320–9327.CrossRefGoogle Scholar
  23. 23.
    M. A. Polovkova, A. G. Martynov, K. P. Birin, S. E. Nefedov, Y. G. Gorbunova, A. Y. Tsivadze, Inorg. Chem., 2016, 55, 9258–9269.CrossRefGoogle Scholar
  24. 24.
    I. V. Nefedova, Y. G. Gorbunova, S. G. Sakharov, A. Y. Tsivadze, Russ. J. Inorg. Chem., 2005, 50, 165–173.Google Scholar
  25. 25.
    D. O. Oluwole, A. V. Yagodin, N. C. Mkhize, K. E. Sekhosana, A. G. Martynov, Y. G. Gorbunova, A. Y. Tsivadze, T. Nyokong, Chem. Eur. J., 2017, 23, 2820–2830.CrossRefGoogle Scholar
  26. 26.
    A. G. Martynov, I. V. Nefedova, Y. G. Gorbunova, A. Y. Tsivadze, Mendeleev Commun., 2007, 17, 66–67.CrossRefGoogle Scholar
  27. 27.
    N. Sheng, R. Li, C.-F. Choi, W. Su, D. K. P. Ng, X. Cui, K. Yoshida, N. Kobayashi, J. Jiang, Inorg. Chem., 2006, 45, 3794–3802.CrossRefGoogle Scholar
  28. 28.
    V. E. Pushkarev, L. G. Tomilova, V. N. Nemykin, Coord. Chem. Rev., 2016, 319, 110–179.CrossRefGoogle Scholar
  29. 29.
    P. Gans, A. Sabatini, A. Vacca, Talanta, 1996, 43, 1739–1753.CrossRefGoogle Scholar
  30. 30.
    Y. G. Gorbunova, A. G. Martynov, A. Y. Tsivadze, in Handbook of Porphyrin Science, Eds K. M. Kadish, K. M. Smith, R. Guilard, World Scientific Publishing, 2012, vol. 24, pp. 271–388.CrossRefGoogle Scholar
  31. 31.
    L. A. Lapkina, V. E. Larchenko, G. A. Kirakosyan, A. Y. Tsivadze, S. I. Troyanov, Y. G. Gorbunova, Inorg. Chem., 2018, 57, 82–85.CrossRefGoogle Scholar
  32. 32.
    R. D. Shannon, Acta Crystallogr., Ser. A, 1976, A32, 751–767.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • A. G. Martynov
    • 1
    Email author
  • A. V. Bykov
    • 2
  • Yu. G. Gorbunova
    • 1
    • 3
  • A. Yu. Tsivadze
    • 1
    • 3
  1. 1.A. N. Frumkin Institute of Physical Chemistry and ElectrochemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.Department of ChemistryLomonosov Moscow State UniversityMoscowRussian Federation
  3. 3.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation

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