Journal of Fluorescence

, Volume 26, Issue 2, pp 585–592 | Cite as

Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State

  • Valery V. Volchkov
  • Fedor E. Gostev
  • Ivan V. Shelaev
  • Viktor A. Nadtochenko
  • Svetlana N. Dmitrieva
  • Sergey P. Gromov
  • Mikhail V. Alfimov
  • Mikhail Ya. Melnikov


Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown. The compounds investigated can be viewed as novel optical molecular sensors for alkali and alkaline-earth metal cations. The photoejection of a metal cation into the bulk was not observed.


Aza-crown ether Complexation Dissociation Perchlorates Transient absorption Recoordination 



Financial support from the Russian Foundation for Basic Research is gratefully acknowledged.


  1. 1.
    Valeur B, Bourson J, Pouget J (1993) Ion recognition detected by changes in photoinduced charge or energy transfer, In: Czarnik AW (ed) Fluorescent chemosensors for ion and molecular recognition. ACS Symposium Series 538, WashingtonGoogle Scholar
  2. 2.
    Gromov SP, Fedorova OA, Alfimov MV, Druzhinin SI, Rusalov MV, Uzhinov BM (1995) Crown-containing styryl dyes. Synthesis, luminescence and complexation of the trans-isomers of chromogenic 15-crown-5 ethers. Russ Chem Bull 44:1922–1928CrossRefGoogle Scholar
  3. 3.
    Druzhinin SI, Rusalov MV, Uzhinov BM, Alfimov MV, Gromov SP, Fedorova OA (1995) Excited state relaxation processes of crowned styryl dyes and their metal complexes. Proc Indian Acad Sci Chem Sci 107:721–727Google Scholar
  4. 4.
    Rusalov MV, Uzhinov BM, Alfimov MV, Gromov SP (2010) Photoinduced recoordination of metal cations in complexes with chromogenic crown ethers. Russ Chem Rev 79:1099–1121CrossRefGoogle Scholar
  5. 5.
    Ushakov EN, Nadtochenko VA, Gromov SP, Vedernikov AI, Lobova NA, Alfimov MV, Gostev FE, Petrukhin AN, Sarkisov OM (2004) Ultrafast excited state dynamics of the bi- and termolecular stilbene-viologen charge-transfer complexes assembles via host-guest interactions. Chem Phys 298:251–261CrossRefGoogle Scholar
  6. 6.
    Freidzon AY, Bagatur’yants AB, Ushakov EN, Gromov SP, Alfimov MV (2011) Ab initio study of the structure, spectral, ionochromic, and fluorochromic properties of benzoazacrown-containing dyes as potential optical molecular sensors. J Quant Chem 111:2649–2662CrossRefGoogle Scholar
  7. 7.
    Lee JH, Lee JH, Choi YR, Kang P, Choi M-G, Jeong K-S (2014) Synthetic K+/Cl-selective symporter across a phospholipid membrane. J Org Chem 79:6403–6409CrossRefPubMedGoogle Scholar
  8. 8.
    Poronik YM, Clermont G, Blanchard-Desce M, Gryko DT (2013) Nonlinear optical chemosensor for sodium ion based on rhodol chromophore. J Org Chem 78:11721–11732CrossRefPubMedGoogle Scholar
  9. 9.
    Gromov SP, Dmitrieva SN, Vedernikov AI, Kurchatov NA, Kuz’mina LG, Sazonov SK, Strelenko YA, Alfimov MV, Howard JAK, Ushakov EN (2013) Synthesis, structure, and characterization of chromo(fluoro)ionophores with cation-triggered emission based on N-methylaza-crown-ether styryl dyes. J Org Chem 78:9834–9847CrossRefPubMedGoogle Scholar
  10. 10.
    Gromov SP, Dmitrieva SN, Vedernikov AI, Kurchatov NA, Kuz’mina LG, Strelenko YA, Alfimov MV, Howard JAK (2009) N-Methylbenzoazacrown ethers with the nitrogen atom conjugated with the benzene ring: the improved synthesis and the reasons for the high stability of complexes with metal and ammonium cations. J Phys Org Chem 22:823–833CrossRefGoogle Scholar
  11. 11.
    Gromov SP, Dmitrieva SN, Vedernikov AI, Kuz’mina LG, Churakov AV, Strelenko YA, Howard JAK (2003) Novel promising benzoazacrown ethers as a result of ring transformation of benzocrown ethers: synthesis, structure and complexation with Ca2+. Eur J Org Chem 16:3189–3199CrossRefGoogle Scholar
  12. 12.
    Dix JP, Vögtle F (1980) Chem Ber 113:457–4470. doi: 10.1002/cber.19801130206 CrossRefGoogle Scholar
  13. 13.
    Melhuish WH (1961) Quantum efficiences of fluorecence of organic substances – effect of solvent and concentration of fluorescence solute. J Phys Chem 65:229–235CrossRefGoogle Scholar
  14. 14.
    Shelaev IV, Gostev FE, Shkuropatov YA, Ptushenko VV, Mamedov MD, Sarkisov MO, Nadtochenko VA, Shuvalov AV (2011) Alternative electron donors in photosystem II core complexes and isolated reaction centers. J Photochem Photobiol B 104:44–50CrossRefPubMedGoogle Scholar
  15. 15.
    Himmelblau DM (1972) Applied nonlinear programming. Mc-Grow-Hill, AustinGoogle Scholar
  16. 16.
    Solov'ev VP (2007) Thermodynamics of supramolecular complexes of crown-ethers and their macrocyclic and acyclic analogues. Dissertation, Lomonosov Moscow State UniversityGoogle Scholar
  17. 17.
    Fery-Forgues S, Le Bris MT, Guetté JP, Valeur B (1988) Ion-responsive fluorescent compounds. 1. Effect of cation binding on photophysical properties of benzoxazinone derivative linked to monoaza-15-crown-5. J Phys Chem 92:6233–6237CrossRefGoogle Scholar
  18. 18.
    Ahrland S, Liljenzin JO, Rydberg J (1973) Comprehensive inorganic chemistry. Pergamon, OxfordGoogle Scholar
  19. 19.
    Vedernikov AI, Dmitrieva SN, Kuzmina LG, Kurchavov NA, Strelenko YA, Howard JAK, Gromov SP (2009) Benzoaza-15-crown-5 ethers: synthesis, structure, and complex formation with metal and ethylammonium ions. Russ Chem Bull 58:978–1001CrossRefGoogle Scholar
  20. 20.
    Echert F, Leito I, Kaljurand I, Kütt A, Klamt A, Diedenhofen M (2009) Prediction of acidity in acetonitrile solution with COSMO-RS. J Comput Chem 30:799–810CrossRefGoogle Scholar
  21. 21.
    Sverdlova OV (1973) Electronic spectra in organic chemistry. Khimiya, St.-PeterburgGoogle Scholar
  22. 22.
    Lippert EZ (1955) Dipolmoment and electronstructur von angeregtan moleculen. Z Naturforsch A 10:1649–1653CrossRefGoogle Scholar
  23. 23.
    Martin MM, Plaza P, Meyer YH, Bégin L, Bourson J, Valeur B (1994) A new concept of photogeneration of cations: evidence for photoejection of Ca2+ and Li+ from complexes with a crown-ether-linked merocyanine by picosecond spectroscopy. J Fluoresc 4:271–273CrossRefPubMedGoogle Scholar
  24. 24.
    Martin MM, Plaza P, Meyer YH, Badaoui F, Bourson J, Lefevre J-P, Valeur B (1996) Steady-state and picosecond spectroscopy of Li+ or Ca2+ complexes with a crowned merocyanine. Reversible photorelease of cations. J Phys Chem 100:6879–6888CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Valery V. Volchkov
    • 1
  • Fedor E. Gostev
    • 2
  • Ivan V. Shelaev
    • 2
  • Viktor A. Nadtochenko
    • 1
    • 2
  • Svetlana N. Dmitrieva
    • 3
  • Sergey P. Gromov
    • 1
    • 3
  • Mikhail V. Alfimov
    • 3
  • Mikhail Ya. Melnikov
    • 1
  1. 1.Chemistry DepartmentM. V. Lomonosov Moscow State UniversityMoscowRussia
  2. 2.N. N. Semenov Institute of Chemical PhysicsRussian Academy of SciencesMoscowRussia
  3. 3.Photochemistry CenterRussian Academy of SciencesMoscowRussia

Personalised recommendations