View PDF Version
 
DOI: 10.1039/A707284H (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 1083-1092

Generation and identification of 1,4-perinaphthadiyl radical cation—first observation of the electronic absorption spectrum of an ionized diradical

(Note: The full text of this document is currently only available in the PDF Version )

Zhendong Zhu, Thomas Bally, Jakob Wirz and Markus Fülscher

Abstract

γ-Irradiation of 6b,7,8,8a-tetrahydrocyclobut[a]acenaphthylene (CAN) in haloalkane glasses at 77 K yields a persistent radical cation, CAN˙+, whose electronic absorption spectrum has been obtained. Irradiation at >640 nm converts this into an isomer which is identical with that formed by ionization of 1,4-dihydro-1,4-ethanonaphtho[1,8-de][1,2]diazepine (END) and subsequent irradiation of the radical cation at λ > 540 nm. In both cases, further irradiation at 450 nm yields the radical cation of 1,8-divinylnaphthalene (DVN˙+) which was identified by ionization of DVN generated in situ by photolysis of CAN. These related observations identify the photoisomer of CAN˙+ as 1,4-perinaphthadiyl radical cation (7,8,9,10-tetrahydrocyclohepta[de]naphthalene-7,10-diylium, CND˙+).

The molecular and electronic structures of all observed radical cations, as well as their electronic absorption spectra, are discussed on the basis of B3LYP and CASPT2 quantum chemical calculations and, in the case of CAN˙+ and DVN˙+, also by reference to the photoelectron spectra of the neutral hydrocarbons. The CAN˙+→PND˙+→DVN˙+ sequence of photoreactions is discussed on the basis of orbital and state correlation diagrams.

References

  1. P. Dowd, J. Am. Chem. Soc., 1966, 88, 2587 CrossRef CAS.
  2. P. Dowd and M. Chow, Tetrahedron, 1982, 38, 799 CrossRef CAS.
  3. M. Rule, A. R. Matlin, D. E. Seeger, E. F. Hilinski, D. A. Dougherty and J. A. Berson, Tetrahedron, 1982, 38, 787 CrossRef CAS.
  4. M. S. Platz, in Diradicals, ed. W. T. Borden, Wiley, New York, 1982 Search PubMed.
  5. J. Wirz, Pure Appl. Chem., 1984, 56, 1289 CrossRef CAS.
  6. C. R. Watson, R. M. Pagni, J. R. Dodd and J. E. Bloor, J. Am. Chem. Soc., 1976, 98, 2551 CrossRef CAS.
  7. M. Gisin, E. Rommel, J. Wirz, M. N. Burnett and R. M. Pagni, J. Am. Chem. Soc., 1979, 101, 2216 CrossRef CAS.
  8. M. N. Burnett, R. Boothe, E. Clark, M. Gisin, H. M. Hassaneen, R. M. Pagni, G. Persy, R. J. Smith and J. Wirz, J. Am. Chem. Soc., 1988, 110, 2527 CrossRef CAS.
  9. L. J. Johnston and J. C. Scaiano, Chem. Rev., 1989, 89, 521 CrossRef CAS.
  10. M. C. Biewer, M. S. Platz, M. Roth and J. Wirz, J. Am. Chem. Soc., 1991, 113, 8069 CrossRef CAS.
  11. S. Pedersen, J. L. Herek and A. H. Zewail, Science, 1994, 266, 1293.
  12. A. H. Zewail, J. Phys. Chem., 1996, 100, 12 701 CrossRef CAS.
  13. C. Doubleday, K. Bolton and W. L. Hase, J. Am. Chem. Soc., 1997, 119, 5251 CrossRef CAS.
  14. J. A. Berson, Acc. Chem. Res., 1997, 30, 238 CrossRef CAS.
  15. W. Adam, W. T. Borden, C. Burda, H. Foster, T. Heidenfelder, M. Heubes, D. A. Hrovat, F. Kita, S. B. Lewis, D. Scheutzow and J. Wirz, J. Am. Chem. Soc., 1998, 120, 593 CrossRef CAS.
  16. W. Adam, H. Platsch and J. Wirz, J. Am. Chem. Soc., 1989, 111, 6896 CrossRef CAS.
  17. E. Hasler, A. Hörmann, G. Persy, H. Platsch and M. Wirz, J. Am. Chem. Soc., 1993, 115, 5400 CrossRef CAS.
  18. D. R. McMasters, J. Wirz and G. J. Snyder, J. Am. Chem. Soc., 1997, 119, 8568 CrossRef CAS.
  19. W. R. Roth, C. U. Unger and T. Wasser, Liebigs Ann. Chem., 1996, 12, 2155 Search PubMed.
  20. F. Williams, J. Chem. Soc., Faraday Trans., 1994, 90, 1681 RSC.
  21. F. Williams, Q.-X. Guo, T. M. Kolb and S. F. Nelsen, J. Chem. Soc., Chem. Commun., 1989, 1835 RSC.
  22. W. Adam, C. Sahin, J. Sendelbach, H. Walter, G.-F. Chen and F. Williams, J. Am. Chem. Soc., 1994, 116, 2576 CrossRef CAS.
  23. K. Komaguchi, M. Shiotani and A. Lund, Chem. Phys. Lett., 1997, 265, 217 CrossRef CAS.
  24. N. L. Bauld and G. R. Stevenson, J. Am. Chem. Soc., 1969, 91, 3675 CrossRef CAS.
  25. F. Gerson, A. de Meijere and X.-Z. Qin, J. Am. Chem. Soc., 1989, 111, 1135 CrossRef CAS.
  26. (a) P. Dowd, J. Am. Chem. Soc., 1970, 92, 1066 CrossRef CAS; (b) P. Dowd, W. Chang and Y. H. Paik, J. Am. Chem. Soc., 1986, 108, 7416 CrossRef CAS.
  27. R. L. Smith and H. Kenttämaa, J. Am. Chem. Soc., 1995, 117, 1393 CrossRef CAS.
  28. K. N. Thoen and H. I. Kenttämaa, J. Am. Chem. Soc., 1997, 119, 3832 CrossRef CAS.
  29. See, for example: P. G. Wenthold, J. Hu and R. R. Squires, J. Am. Chem. Soc., 1996, 118, 11 865 Search PubMed.
  30. P. G. Wenthold, J. Hu, R. R. Squires and W. C. Lineberger, J. Am. Chem. Soc., 1996, 118, 475 CrossRef CAS.
  31. P. G. Wenthold, J. B. Kim and W. C. Lineberger, J. Am. Chem. Soc., 1997, 119, 1354 CrossRef CAS.
  32. T. Bally, in Radical Ionic Systems (Top. Mol. Organization Eng., Vol. 6), ed. A. Lund and M. Shiotani, Kluwer, Dordrecht, 1991, pp. 3–54 Search PubMed.
  33. T. Bally, Chimia, 1994, 48, 378 CAS.
  34. T. Bally, L. Truttmann, J. T. Wang and F. Williams, J. Am. Chem. Soc., 1995, 117, 7923 CrossRef CAS.
  35. H. Weng, C. Scarlata and H. D. Roth, J. Am. Chem. Soc., 1996, 118, 10 947 CrossRef CAS.
  36. C. Sandorfy, Can. J. Spectrosc., 1965, 85, 10 Search PubMed.
  37. A. Grimison and G. A. Simpson, J. Phys. Chem., 1968, 72, 1776 CrossRef CAS.
  38. T. Shida and W. H. Hamill, J. Am. Chem. Soc., 1966, 88, 5371 CrossRef CAS.
  39. T. Shida and W. H. Hamill, J. Chem. Phys., 1968, 44, 4372 CrossRef.
  40. R. Dressler, L. Neuhaus and M. Allan, J. Electron Spectr. Relat. Phenom., 1983, 31, 181 Search PubMed.
  41. A. D. Becke, Phys. Rev. A, 1988, 39, 3098 CrossRef.
  42. A. D. Becke, J. Chem. Phys., 1993, 98, 5648 CrossRef CAS.
  43. C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785 CrossRef CAS.
  44. For a description of the density functionals implemented into the GAUSSIAN program 45, see: B. G. Johnson, P. M. W. Gill and J. A. Pople, J. Chem. Phys., 1993, 98, 5612 Search PubMed.
  45. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montogomery, 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. Repogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. DeFrees, J. Baker, J. P. Stewart, M. Head-Gordon, M. C. Gonzales and J. A. Pople. GAUSSIAN Program; GAUSSIAN 94, Rev. B1 and D4; Gaussian, Inc., Pittsburgh, PA, 1995.
  46. K. Andersson and B. O. Roos, in Modern Electronic Structure Theory, Part 1, Vol. 2, World Scientific., Singapore, 1995, pp. 55 Search PubMed.
  47. K. Andersson, M. R. A. Blomberg, M. P. Fülscher, V. Kellö, R. Lindh, P.-Å. Malmqvist, J. Noga, J. Olson, B. O. Roos, A. Sadlej, P. E. M. Siegbahn, M. Urban and P.-O. Widmark, MOLCAS 3, University of Lund, Sweden, 1994.
  48. M. P. Fülscher, S. Matzinger and T. Bally, Chem. Phys. Lett., 1995, 236, 167 CrossRef.
  49. T. Bally, C. Carra, Z. Zhu and M. Fülscher, unpublished results.
  50. P.-O. Widmark, P.-Å. Malmqvist and B. O. Roos, Theor. Chim. Acta, 1990, 77, 291 CAS.
  51. M. C. Zerner and J. E. Ridley, Theor. Chim. Acta, 1973, 32, 111 CrossRef CAS.
  52. M. C. Zerner. ZINDO; Quantum Theory Project, University of Florida, Gainesville.
  53. T. Bally, B. Albrecht, S. Matzinger and M. G. Sastry, MOPLOT, a program for displaying results of LCAO-MO calculations, available from Thomas.Bally@unifr.ch on request, University of Fribourg, 1997.
  54. E. Haselbach and A. Schmelzer, Helv. Chim. Acta, 1979, 54, 1299 CrossRef.
  55. R. Gleiter, W. Schaefer and M. Eckert-Maksic, Chem. Ber., 1981, 114, 2309 CAS.
Click here to see how this site uses Cookies. View our privacy policy here.