Skip to main content
SpringerLink
Log in

EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge

  • Published:
Applied Magnetic Resonance Aims and scope Submit manuscript

Abstract

Two short nitroxide biradicals of similar composition, R6′–R6′ (B0) and R6′–(C ≡ C)–R6′ (B1), where R6′ is 1-oxyl-2,2,6,6-tetramethyl-3,4-ene-nitroxide ring, have been investigated by electron paramagnetic resonance spectroscopy and X-ray structural analysis. Quantum chemical calculations at UDFT/B3LYP/cc-pVDZ level were also performed and compared with the X-ray structural data. Zero-field splitting parameters D for B0 and B1 were found to be equal −0.0048 and −0.0022 cm−1, respectively, in good agreement with quantum chemical prediction. Potential energy surface scans corresponding to pathways of the conformational rearrangements were calculated; rotation barriers for B0 and B1 were found to be 19.2 and 4.0 kJ/mol, respectively; and structural rigidity and probable differences in biradicals behavior are discussed. Calculations of spin density distribution in biradicals B0 and B1 were also carried out.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. E.G. Rozantsev, Free Nitroxyl Radicals (Plenum Press, New York, 1970)

    Book  Google Scholar 

  2. V.N. Parmon, A.I. Kokorin, G.M. Zhidomirov, Stable Biradicals (Nauka, Moscow, 1980)

    Google Scholar 

  3. E.G. Rozantsev, R.I. Zhdanov (eds.), Nitroxide Radicals. Synthesis, Chemistry, Applications (Nauka, Moscow, 1987)

  4. L.B. Volodarsky (ed.), Nitroxide. Synthesis, Properties, Applications, vol. 1–2 (CRC Press, Boca Raton, 1988)

    Google Scholar 

  5. R.I. Zhdanov (ed.), Bioactive Spin Labels (Springer, Berlin, 1992)

    Google Scholar 

  6. A. Rassat, Pure Appl. Chem. 62, 223 (1990)

  7. A.I. Kokorin, Appl. Magn. Reson. 26, 253 (2004)

    Article  Google Scholar 

  8. J. Fritscher, M. Beyer, O. Schiemann, Chem. Phys. Lett. 364, 393 (2002)

    Article  ADS  Google Scholar 

  9. M. Abe, Chem. Rev. 113, 7011 (2013)

    Article  Google Scholar 

  10. A.B. Shapiro, M.G. Goldfield, E.G. Rozantsev, Tetrahedron Lett. 14, 2183 (1973)

  11. V.V. Pavlikov, A.B. Shapiro, E.G. Rozantsev, Izv. AN SSSR, Ser. Khim. No. 1, 128 (1980)

  12. V.V. Pavlikov, V.V. Muraviev, A.B. Shapiro, Izv. AN SSSR, Ser. Khim. No. 5, 1200 (1980)

  13. S. Torii, T. Hase, M. Kuroboshi, C. Amatore, A. Jutand, H. Kawafuchi, Tetrahedron Lett. 38, 7391 (1997)

  14. E.G. Rozantsev, O.A. Ozhogina, R.R. Rakhimov, A.I. Prokof’ev, Mol. Phys. 76, 1009 (1992)

    Article  ADS  Google Scholar 

  15. A.I. Kokorin, V.V. Pavlikov, A.B. Shapiro, Proc. Acad. Sci. USSR, Doklady Phys. Chem. 253, 147 (1980)

    Google Scholar 

  16. A.B. Shapiro, V.N. Parmon, V.V. Pavlikov, V.I. Rubtsov, E.G. Rozantsev, Izv. AN SSSR, Ser. Khim. No. 2, 449 (1980)

  17. A.I. Kokorin, V.A. Tran, K. Rasmussen, G. Grampp, Appl. Magn. Reson. 30, 35 (2006)

    Article  Google Scholar 

  18. V.A. Tran, A.I. Kokorin, G. Grampp, K. Rasmussen, Appl. Magn. Reson. 35, 389 (2009)

    Article  Google Scholar 

  19. A.I. Kokorin, E.N. Golubeva, B. Mladenova, V.A. Tran, T. Kalai, K. Hideg, G. Grampp, Appl. Magn. Reson. 44, 1041 (2013)

    Article  Google Scholar 

  20. A.I. Kokorin, S. Landgraf, A.B. Shapiro, G. Grampp, Appl. Magn. Reson. 45, 125 (2014)

    Article  Google Scholar 

  21. S. Ya, Umanskiy, E.N. Golubeva, B.N. Plakhutin. Russ. Chem. Bull. 62(7), 1511–1518 (2013)

    Article  Google Scholar 

  22. T. Kálai, J. Jeko, Z. Berente, K. Hideg, Synthesis. 38, 439 (2006)

    Google Scholar 

  23. M.J.D. Powell, Acta Numerica 7, 287–336 (1998)

  24. S.G. Johnson, The NLopt nonlinear-optimization package (2013), http://ab-initio.mit.edu/nlopt

  25. S.G. Johnson, A. Cervellino, J. Wuttke, libcerf, numeric library for complex error functions (2012), http://apps.jcns.fz-juelich.de/libcerf

  26. G.R. Luckhurst, G.F. Pedulli, Mol. Phys. 20(6), 1043–1055 (1971)

    Article  ADS  Google Scholar 

  27. G.M. Sheldrick, SADABS, v. 2.03, Bruker/Siemens Area Detector Absorption Correction Program (Bruker AXS, Madison, 2003)

    Google Scholar 

  28. G.M. Sheldrick, Acta Cryst. A64, 112 (2008)

    Article  Google Scholar 

  29. F. Neese, The ORCA program system, Wiley Interdiscip. Rev. Comput. Mol. Sci. 2, 73–78 (2012)

    Article  Google Scholar 

  30. T.H. Dunning Jr., J. Chem. Phys. 90, 1007–1023 (1989)

  31. L. Noodleman, J. Chem. Phys. 74, 5737–5743 (1981)

    Article  ADS  Google Scholar 

  32. L. Noodleman, E.R. Davidson, Chem. Phys. 109, 131–143 (1986)

    Article  ADS  Google Scholar 

  33. F. Neese, J. Chem. Phys. 127, 164112 (2007)

    Article  ADS  Google Scholar 

  34. S. Sinnecker, A. Rajendran, A. Klamt, M. Diedenhofen, F. Neese, J. Phys. Chem. A 110, 2235–2245 (2006)

    Article  Google Scholar 

  35. A.I. Kokorin, B. Mladenova, E.N. Golubeva, G. Grampp, Appl. Magn. Reson. 41, 353 (2011)

    Article  Google Scholar 

  36. A.I. Kokorin, V.N. Parmon, A.A. Shubin, Atlas of Anisotropic EPR Spectra of Nitroxide Biradicals (Nauka, Moscow, 1984)

  37. V. Sadovnichy, A. Tikhonravov, Vl. Voevodin, V. Opanasenko, in Contemporary High Performance Computing: From Petascale toward Exascale (Chapman & Hall/CRC Computational Science), (CRC Press, Boca Raton, 2013) pp. 283–307

Download references

Acknowledgments

This work is supported in part by the Russian Foundation for Basic Research (project no. 12-03-00623-a) and by the Hungarian Research Fund (Grant OTKA K 81123). Calculations were performed using resources of the Supercomputing Center of the Lomonosov Moscow State University [37].

Author information

Authors and Affiliations

  1. Chemistry Department, M. Lomonosov Moscow State University, 11991, Leninskiye Gory 1-3, Moscow, Russian Federation

    O. I. Gromov & E. N. Golubeva

  2. Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilov St., 28, Moscow, Russian Federation

    V. N. Khrustalev

  3. Institute of Organic and Medical Chemistry, University of Pécs, PO Box 99, Pécs, H-7602, Hungary

    T. Kálai & K. Hideg

  4. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russian Federation

    A. I. Kokorin

Authors
  1. O. I. Gromov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. N. Golubeva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. N. Khrustalev
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. T. Kálai
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. K. Hideg
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. I. Kokorin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to A. I. Kokorin.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gromov, O.I., Golubeva, E.N., Khrustalev, V.N. et al. EPR, the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge. Appl Magn Reson 45, 981–992 (2014). https://doi.org/10.1007/s00723-014-0573-z

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00723-014-0573-z

Keywords

Search

Navigation