Skip to main content
Log in

Nature of intermolecular interactions and conductance in a system consisting of alkali metal ions, crown ether, anion radicals, and a polar solvent

  • Published:
Theoretical and Experimental Chemistry Aims and scope

Abstract

The methods of23Na and7Li NMR, EPR and conductimetry have been used to investigate the intermolecular interactions in systems consisting of the anion-radical salt of an alkali metal and a crown ether, dissolved in acetonitrile. Relations have been established between the structure of the complexes formed in solution, their magnetic resonance characteristics, and their limiting conductance. For solutions of anionradical salts in the presence of an excess of crown ether additional routes for conductance have been identified, connected with electron exchange reactions between the molecules of organic π-acids in different charge states.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

Literature cited

  1. V. S. Kuts and O. V. Zhalko-Titarenko, “The effect of complex formation on the electrical conductivity in systems consisting of anion radical salt, crown ether and polar solvent,” Teor. Éksp. Khim.,22, No. 2, 188–196 (1986).

    Google Scholar 

  2. J. Takada, H. Jano, M. Ishimashi, and H. Isozumi, “A conductance study of alkalimetal ion 15-crown-5 and dibenzo-24-crown-8 complexes in propylene carbonate,” Bull. Chem. Soc. Jpn.,53, No. 1, 72–76 (1980).

    Google Scholar 

  3. R. C. Phillips, S. Khazaeli, and J. L. Dye, “Sodium-23 NMR study of sodium bromide in methylamine solutions that contain macrocyclic polyethers,” J. Phys. Chem.,89, No. 4, 600–606 (1985).

    Google Scholar 

  4. Ch. A. Kraus and R. M. Fuoss, “The evaluation of λ and K for incompletely dissociated electrolytes,” J. Am. Chem. Soc.,55, No. 2, 476–491 (1933).

    Google Scholar 

  5. A. S. Weissberger, E. G. Proskauer, J. A. Riddick, and E. E. Toops, Organic Solvents: Physical Properties and Methods of Purification [Russian translation], Izd. Inostr. Lit., Moscow (1958).

    Google Scholar 

  6. A. A. Egorenkov, Yu. V. Mitnik, M. A. Alesherov, and T. M. Guseinova, “The purification of crown ethers” [in Russian], Dep. VINITI April 2, 1984, No. 1832, Moscow (1984).

  7. D. S. Acher, R. J. Harder, W. R. Hertler, et al., “7,7', 8,8'-Tetracyanoquinodimethane and its electrically conducting anion derivatives,” J. Am. Chem. Soc.,82, No. 24, 6408–6409 (1960).

    Google Scholar 

  8. J. A. Pople and G. A. Segal, “Approximate self consistent molecular orbital theory. 3. CNDO results for AB2 and AB3 systems,” J. Chem. Phys.,44, No. 9, 3289–3296 (1966).

    Google Scholar 

  9. J. D. Lin and A. I. Popov, “NMR studies of some sodium ion complexes with crown ethers and [2.2.2]cryptands in various solvents,” J. Am. Chem. Soc.,103, No. 13, 3773–3777 (1981).

    Google Scholar 

  10. T. Takeshita and N. Hirota, “Signs of alkali metal splittings and the structure of ion pair radical ions,” Chem. Phys. Lett.,4, No. 6, 369–372 (1969).

    Google Scholar 

  11. J. Berts and J. Bolton, Theory and Practical Applications of the EPR Method [Russian translation], Izd. Mir, Moscow (1975).

    Google Scholar 

  12. V. S. Kuts and Yu. A. Kruglyak, “The analysis of poorly resolved EPR Spectra of free radicals. Radiospectroscopic and quantum-chemical methods of investigating molecular structure,” [in Russian], pp. 157–164, Izd. Nauka, Moscow (1967).

    Google Scholar 

  13. Z. G. Soos, Organic Molecular Crystals: Charge-Transfer Complexes. Treatise on Solid State Chemistry, Vol. 3, pp. 679–767 (1976).

    Google Scholar 

  14. J. G. Sharp and M. C. R. Symons, Investigation of Ion Pairs by the Method of Paramagnetic Resonance. Ions and Ion Pairs in Organic Reactions [Russian translation], Izd. Mir, Moscow (1975), pp. 196–291.

    Google Scholar 

  15. K. I. Zamaraev, Yu. N. Molin, and K. M. Salikhov, Spin Exchange. Theory and Physicochemical Applications [in Russian], Izd. Nauka, Novosibirsk (1977).

    Google Scholar 

  16. V. É. Kampar, S. P. Valtere, and O. Ya. Neiland, “Determination from IR spectra of the extent of charge transfer in π-π complexes of 7,7', 8,8'-tetracyanoquinodimethane,” Teor. Éksp. Khim.,14, No. 3, 369–373 (1978).

    Google Scholar 

  17. I. Ruff and V. J. Friedrich, “Transfer diffusion. 1. Theoretical,” J. Phys. Chem.,75, No. 21, 3297–3302 (1971).

    Google Scholar 

  18. K. Suga, T. Yorifuji, and Sh. Acyadni, “Verification of the transfer diffusion theory by electric conductivity measurement,” Electrochem. Acta,27, No. 9, 1259–1261 (1982).

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Additional information

Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 173–182, March–April, 1989.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kuts, V.S., Zhalko-Titarenko, O.V., Tsekhmistrenko, L.F. et al. Nature of intermolecular interactions and conductance in a system consisting of alkali metal ions, crown ether, anion radicals, and a polar solvent. Theor Exp Chem 25, 158–165 (1989). https://doi.org/10.1007/BF01135005

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01135005

Keywords

Navigation