Russian Chemical Bulletin

, Volume 55, Issue 9, pp 1593–1597 | Cite as

Photochemical synthesis and properties of quintet pyridyl-2,6-dinitrenes

  • S. V. Chapyshev


The structures and properties of quintet pyridyl-2,6-dinitrenes formed by low-temperature photolysis of 2,6-diazidopyridines were studied by ESR and quantum chemical (B3LYP/6-31G*) methods. The synthesized dinitrenes represent a new type of quintet tetraradicals for which the ratio of zero-field splitting parameters is ¦ E q¦/¦D q¦ = 1/3. This ratio is characteristic of quintet molecules in which the vector angle between two biradical centers is close to 114.5°.

Key words

azides nitrenes photolysis ESR high-spin states 


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  1. 1.
    L. A. Buchachenko, Usp. Khim., 1990, 59, 529 [Russ. Chem. Rev., 1990, 59 (Engl. Transl.)].Google Scholar
  2. 2.
    K. Itoh and M. Kinoshita, Molecular Magnets: New Magnetic Materials, Kodansha-Godon and Breach, Tokyo, 2000.Google Scholar
  3. 3.
    J. S. Miller and M. Drillon, Magnetism: Molecules to Materials. Molecular Based Materials, Wiley, Wein Leim, 2001, 3.Google Scholar
  4. 4.
    A. Rajca, Chem. Rev., 1994, 94, 871.CrossRefGoogle Scholar
  5. 5.
    J. S. Miller and A. J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385.CrossRefGoogle Scholar
  6. 6.
    Magnetic Properties of Organic Materials, Ed. P. M. Lahti, Marcel Dekker, New York, 1999.Google Scholar
  7. 7.
    W. Weltner, Jr., Magnetic Atoms and Molecules, Dover Publications, New York, 1989.Google Scholar
  8. 8.
    H. Oka, Y. Miura, and Y. Teki, Mol. Cryst. Liq. Cryst., 1999, 334, 41.Google Scholar
  9. 9.
    Y. Miura, H. Oka, and Y. Teki, Bull. Chem. Soc. Jpn, 2001, 74, 385.CrossRefGoogle Scholar
  10. 10.
    R. S. Kalgutkar and P. M. Lahti, J. Am. Chem. Soc., 1997, 119, 8784.CrossRefGoogle Scholar
  11. 11.
    R. S. Kalgutkar and P. M. Lahti, Tetrahedron Lett., 2003, 44, 2625.CrossRefGoogle Scholar
  12. 12.
    S. Murata and H. Iwamura, J. Am. Chem. Soc., 1991, 113, 5547.CrossRefGoogle Scholar
  13. 13.
    C. Ling, M. Minato, P. M. Lahti, and H. van Willigen, J. Am. Chem. Soc., 1992, 114, 9959.CrossRefGoogle Scholar
  14. 14.
    T. A. Fukuzawa, K. Sato, A. S. Ichimura, T. Kinoshita, T. Takui, K. Itoh, and P. M. Lahti, Mol. Cryst. Liq. Cryst., 1996, 278, 253.Google Scholar
  15. 15.
    P. M. Lahti, M. Minato, and C. Ling, Mol. Cryst. Liq. Cryst., 1995, 271, 147.Google Scholar
  16. 16.
    T. Nakai, K. Sato, D. Shiomi, T. Takui, K. Itoh, M. Kozaki, and K. Okada, Mol. Cryst. Liq. Cryst., 1999, 334, 157.Google Scholar
  17. 17.
    S. V. Chapyshev, R. Walton, J. A. Sanborn, and P. M. Lahti, J. Am. Chem. Soc., 2000, 122, 1580.CrossRefGoogle Scholar
  18. 18.
    S. V. Chapyshev and H. Tomioka, Bull. Chem. Soc. Jpn, 2003, 76, 2075.CrossRefGoogle Scholar
  19. 19.
    S. V. Chapyshev, R. Walton, P. R. Serwinski, and P. M. Lahti, J. Phys. Chem. A., 2004, 108, 6643.CrossRefGoogle Scholar
  20. 20.
    S. V. Chapyshev, Izv. Akad. Nauk, Ser. Khim., 2006, 55, 1085 [Russ. Chem. Bull., Int. Ed., 2006, 55, 1126].Google Scholar
  21. 21.
    S. V. Chapyshev, Mendeleev Commun., 1999, 164.Google Scholar
  22. 22.
    S. V. Chapyshev and M. S. Platz, Mendeleev Commun, 2001, 56.Google Scholar
  23. 23.
    S. Mossin, H. Weihe, and A.-L. Barra, J. Am. Chem. Soc., 2002, 124, 8764.CrossRefGoogle Scholar
  24. 24.
    M. J. Frish, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Peterson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople, Gaussian 94. Revision D.4. Gaussian Inc., Pittsburgh PA, 1995.Google Scholar
  25. 25.
    S. V. Chapyshev, Mendeleev Commun., 2002, 227.Google Scholar
  26. 26.
    S. V. Chapyshev, Mendeleev Commun., 2003, 53.Google Scholar

Copyright information

© Springer Science+Business Media, Inc. 2006

Authors and Affiliations

  • S. V. Chapyshev
    • 1
  1. 1.Institute of Problems of Chemical PhysicsRussian Academy of SciencesChernogolovka, Moscow RegionRussian Federation

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