Stone-wales rearrangements involving heptagonal defects

Fullerene Science and Technology

Volumn 4, Issue 5, 1996, Pages 939-961

  Osawa, Eiji ^a   Honda, Kazuhiko ^a  

^a TOYOHASHI UNIVERSITY OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CONFORMATIONS; DEFECTS; MOLECULAR DYNAMICS; NUMERICAL METHODS;

MOLECULAR ORBITAL METHOD; PYRACYLENE REARRANGEMENT; STONE-WALES REARRANGEMENTS;

FULLERENES;

EID: 0030246590     PISSN: 1064122X     EISSN: None     Source Type: Journal    
DOI: 10.1080/10641229608001154     Document Type: Article

References (21)

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3. (a) Terrones, M.; Terrones, H. Fullerene Sci. Technol. in press.
4. (b) Brabec, C. J.; Maiti, A.; Bernholc, J. Chem. Phys. Lett. 1994, 219, 473.
5. (c) Fujita, M.; Yoshida, M.; Osawa, E. Fullerene Sci. Technol 1995, 3, 93.
6. (a) Ōsawa, E. and Honda, K. in 'Advances in the Chemistry and Physics of Fullerenes and Related Materials, ' Kadish, K. M., and Ruoff, R. S. (Eds.), Vol. 2, The Electrochemical Society: Pennington, N. J. 1995.
7. (b) Honda, K., Osawa, E., Slanina, Z., and Matsumoto, T. Fullerene Sci. Technol. in press.
8. Murry, R. L., Strout, D. L., Odom, G. K. and Scuseria, G. E. Nature 1993, 366, 665.
9. (a) Dewar, M. J. S., Zoebisch, E. G., Healy, E. F. and Stewart, J. J. P. J. Am. Chem. Soc., 1985, 107, 3902.
10. (b) MOPAC93 version 6.01 by J. J. P. Stewart was obtained from the Japan Chemistry Program Exchange, 1-7-12 Nishine-Nishi, Tsuchiura 300, Japan (FAX x-81-298-30-4162), program No. P049.
11. Murry, R. L., Strout, D. L., and Scuseria, G. E. Int. J. Mass Spectry. Ion Process 1994, 138, 113.
12. 3 would be readily removed during the rearrangement process.
13. If an azulene unit is moved to and eventually fused with another azulene unit, a (5 5 7 7) defect is produced.
14. To the authors' knowledge this molecule is still unknown, but AM1-RHF calculation produced a perfectly planar molecule having a closed shell electronic structure (HOMO -7.901 eV, LUMO -0.991 eV). The calculated heat of formation of 105.75 kal/mol as well as the HOMO-LUMO positioins are intermediate between pyrene (67.16 kal/mol, HOMO -8.132 eV, LUMO -0.880 eV) and azupyrene (134.00 kcal/mol, HOMO -7.448 eV, LUMO -1.030 eV). Like its aromatic kins, 11 may also belong to the class of novel Hückel aromatic molecules containing a concentric node separating 14 π-electron periphery from 2 π-electron core (vide infra).
15. Anderson, A. G. Jr., Critchlow, S. C., Andrews, L. C., and Haddock, R. D. Acta Cryst. 1990, C46, 439.
16. Subscript to M or T refer to one of the six different possibilities of bond migration shown in Scheme 3.
17. IUPAC name: dicyclopenta(ef,kl)heptalene. See Anderson, A. G. Jr. Trends in Organic Chemistry 1992, 3, 315.
18. Due to the possibility of a biradical intermediate along the in-plane route, we have performed UHF calculations as well. The first transition state turned out to have a low-energy structure (107.51 kcal/mol relative to azupyrene), but other stationary points have not reached SCF.
19. Anderson, A. G. Jr.; Kao, L. G. J. Org. Chem. 1982, 47, 3589.
20. Anderson, A. G. Jr.; Haddock, R. D. J. Org. Chem. 1991, 56, 550.
21. 16 proposed two mechanisms based on the labeling experiment (Schemes I and II) :