Isolable Polyradical Cations of Polyphenylenediamines with Populated High-Spin States

Journal of Organic Chemistry

Volumn 62, Issue 3, 1997, Pages 448-449

  Stickley, Kurt R ^a   Selby, Trent D ^b   Blackstock, Silas C ^b  

^a VANDERBILT UNIVERSITY   (United States)

^b UNIVERSITY OF ALABAMA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001169834     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9619950     Document Type: Article

References (28)

1. For some reviews of organic molecule-based magnets see: (a) Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179-253. (b) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88. (c) Miller, J. S.; Epstein, A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385. (d) Rajca, A. Chem. Rev. 1994, 94, 871.
2. For some reviews of organic molecule-based magnets see: (a) Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179-253. (b) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88. (c) Miller, J. S.; Epstein, A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385. (d) Rajca, A. Chem. Rev. 1994, 94, 871.
3. For some reviews of organic molecule-based magnets see: (a) Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179-253. (b) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88. (c) Miller, J. S.; Epstein, A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385. (d) Rajca, A. Chem. Rev. 1994, 94, 871.
4. For some reviews of organic molecule-based magnets see: (a) Iwamura, H. Adv. Phys. Org. Chem. 1990, 26, 179-253. (b) Dougherty, D. A. Acc. Chem. Res. 1991, 24, 88. (c) Miller, J. S.; Epstein, A. J. Angew. Chem., Int. Ed. Engl. 1994, 33, 385. (d) Rajca, A. Chem. Rev. 1994, 94, 871.
5. Stickley, K. R.; Blackstock, S. C. J. Am. Chem. Soc. 1994, 116, 11576.
6. Trication triradical lifetimes are milliseconds to minutes at 195 K. See: (a) Stickley, K. R.; Blackstock, S. C. Tetrahedron Lett. 1995, 36, 1585. (b) Stickley, K. R.; Blackstock, S. C. Mol. Cryst. Liq. Cryst. 1995, 272, 81.
7. Trication triradical lifetimes are milliseconds to minutes at 195 K. See: (a) Stickley, K. R.; Blackstock, S. C. Tetrahedron Lett. 1995, 36, 1585. (b) Stickley, K. R.; Blackstock, S. C. Mol. Cryst. Liq. Cryst. 1995, 272, 81.
8. For triarylamine radical cation properties see (a) Hagopian, L.; Günter, K.; Walter, R. I. J. Phys. Chem. 1967, 71, 2290. (b) Seo, E. T.; Nelson, R. F.; Fritsch, J. M.; Marcoux, L. S.; Leedy, D. W.; Adams, R. N. J. Am. Chem. Soc. 1966, 88, 3498.
9. For triarylamine radical cation properties see (a) Hagopian, L.; Günter, K.; Walter, R. I. J. Phys. Chem. 1967, 71, 2290. (b) Seo, E. T.; Nelson, R. F.; Fritsch, J. M.; Marcoux, L. S.; Leedy, D. W.; Adams, R. N. J. Am. Chem. Soc. 1966, 88, 3498.
10. For a description of some isolable neutral quartet organic molecules see: (a) Veciana, J.; Rovira, C.; Ventosa, N.; Crespo, M. I.; Palacio, F. J. Am. Chem. Soc. 1993, 115, 57. (b) Kanno, P.; Inoue, K.; Koga, N.; Iwamura, H. J. Phys. Chem. 1993, 97, 13267. (c) Rajca, A.; Utamapanya, S. J. Am. Chem. Soc. 1993, 115, 2396. (d) Weissman, S. I.; Kothe, G. J. Am. Chem. Soc. 1975, 97, 2537.
11. For a description of some isolable neutral quartet organic molecules see: (a) Veciana, J.; Rovira, C.; Ventosa, N.; Crespo, M. I.; Palacio, F. J. Am. Chem. Soc. 1993, 115, 57. (b) Kanno, P.; Inoue, K.; Koga, N.; Iwamura, H. J. Phys. Chem. 1993, 97, 13267. (c) Rajca, A.; Utamapanya, S. J. Am. Chem. Soc. 1993, 115, 2396. (d) Weissman, S. I.; Kothe, G. J. Am. Chem. Soc. 1975, 97, 2537.
12. For a description of some isolable neutral quartet organic molecules see: (a) Veciana, J.; Rovira, C.; Ventosa, N.; Crespo, M. I.; Palacio, F. J. Am. Chem. Soc. 1993, 115, 57. (b) Kanno, P.; Inoue, K.; Koga, N.; Iwamura, H. J. Phys. Chem. 1993, 97, 13267. (c) Rajca, A.; Utamapanya, S. J. Am. Chem. Soc. 1993, 115, 2396. (d) Weissman, S. I.; Kothe, G. J. Am. Chem. Soc. 1975, 97, 2537.
13. For a description of some isolable neutral quartet organic molecules see: (a) Veciana, J.; Rovira, C.; Ventosa, N.; Crespo, M. I.; Palacio, F. J. Am. Chem. Soc. 1993, 115, 57. (b) Kanno, P.; Inoue, K.; Koga, N.; Iwamura, H. J. Phys. Chem. 1993, 97, 13267. (c) Rajca, A.; Utamapanya, S. J. Am. Chem. Soc. 1993, 115, 2396. (d) Weissman, S. I.; Kothe, G. J. Am. Chem. Soc. 1975, 97, 2537.
14. For a previous preparation see: Ishikawa, W.; Noguchi, K.; Kuwabara ,Y.; Shirota, Y. Adv. Mater. 1993, 5, 559.
15. Buu-Hoï, N. P. J. Chem. Soc. 1952, 4346.
16. -) is a shock-sensitive explosive solid and should be handled with due care. For preparation and properties see: Murata, Y.; Shine, H. J. J. Org. Chem. 1969, 34, 3368.
17. Generally, 5% trifluoroacetic acid and 5% trifluoroacetic anhydride is added to the solvent to quench trace nucleophiles such as water, which tend to decompose the electrophilic polyradical cations.
18. (a) Luckhurst, G. R.; Pedulli, G. F.; Tiecco, M. J. Chem. Soc. B 1971, 329.
19. (b) Kothe, G.; Denkel, K.; Sümmermann, W. Angew. Chem., Int. Ed. Engl. 1970, 9, 906.
20. This transition is expected to be quite weak and difficult to observe. Yoshizawa, K.; Chano, A.; Ito, A.; Tanaka, K.; Yamabe, T.; Fujita, H.; Yamauchi, J.; Shiro, M. J. Am. Chem. Soc. 1992, 114, 5994.
21. Kothe, G.; Ohmes, E.; Brickmann, J.; Zimmermann, H. Angew. Chem., Int. Ed. Engl 1971, 10, 938.
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24. eff 3.92 (3.87 theoretical)] were also determined to demonstrate the viability of the NMR shift method under our conditions.
25. L is the mole fraction of the low spin-state population in the sample.
26. It should be noted that the triplet state is statistically favored over the singlet state by a factor of 3 and that the quartet state is similarly favored over the doublet state by a factor of 2.
27. 1 of a single phenylenediamine unit or ∼ 11.5 kcal/mol according to Figure 1. This energetic requirement would appear to rule out the latter electronic configuration as a major contributor to the doublet trication structures.
28. 3 has been established by C, H, N combusion analysis.