6924
W. Gu, R. G. Weiss / Tetrahedron 56 (2000) 6913±6925
Immegut, E. H.; Grulke, E. A. Polymer Handbook, 4th ed.; Wiley:
New York, 1999; V/21.
1H, J7.2 Hz, CHCH3NpPh), 1.76 ppm (d, 3H, J7.2 Hz,
CHCH3NpPh); mass m/z calculated for C18H16 232, found
232.
16. Talhavini, M.; Atvars, T. D. Z.; Cui, C.; Weiss, R. G. Polymer
1996, 37, 4365.
17. Gu, W.; Hill, A. J.; Wang, X.; Cui, C.; Weiss, R. G. Macro-
molecules, submitted for publication.
References
18. (a) Zavitsas, A. A.; Chatgilialuglu, C. J. Am. Chem. Soc. 1995,
117, 10645. (b) Franz, J. A.; Alnajjar, M. S.; Barrows, R. D.;
Kaisaki, D. L.; Camaioni, D. M.; Suleman, N. K. J. Org. Chem.
1986, 51, 1446.
1. (a) Weiss, R. G.; Ramamurthy, V.; Hammond, G. S. Acc. Chem.
Res. 1993, 26, 530. (b) Ramamurthy, V.; Weiss, R. G.; Hammond,
G. S. In Advances in Photochemistry; Volman, D. H., Neckers, D.,
Hammond, G. S., Eds.; Wiley-Interscience: New York, 1993; Vol.
18, p 67.
19. Moore, W. M.; Hammond, G. S.; Foss, R. P. J. Am. Chem. Soc.
1961, 83, 2789.
20. Leigh, W.; Arnold, D. R. J. Chem. Soc., Chem. Commun.
1980, 406.
2. (a) Cui, C.; Naciri, J.; He, Z.; Costantino, R. M.; Lu, L.;
Hammond, G. S.; Weiss, R. G. Quimica Nova 1993, 16, 578.
(b) Naciri, J.; He, Z.; Costantino, R. M.; Lu, L.; Hammond,
G. S.; Weiss, R. G. In Multidimensional Spectroscopy of Polymers;
Urban, M. W., Provder, T., Eds.; American Chemical Society:
Washington, 1995; Chapter 25.
21. Bellus, D. Adv. Photochem. 1971, 8, 109 (and references cited
therein).
22. Meranda, M. A. Handbook of Organic Photochemistry and
Photobiology; Horspool, W. M., Song, P.-S., Eds.; CRC: Boca
Raton, 1995; Chapter 47.
3. Franck, J.; Rabinowitch, E. Trans. Faraday Soc. 1934, 30, 120
and subsequent papers in the series.
23. Sternberg, V. I. Organic Photochemistry; Chapman, O. L.,
Ed.; Arnold: New York, 1967.
4. See for instance: (a) Fletcher, B.; Suleman, N. K.; Tanko, J. M.
J. Am. Chem. Soc. 1998, 120, 11839. (b) Male, J. L.; Lindfors,
B. E.; Covert, K. J.; Tyler, D. R. J. Am. Chem. Soc. 1998, 120,
13176. (c) Koenig, T. W.; Hay, B. P.; Finke, R. G. Polyhedron
1988, 7, 1499.
24. Gritsan, N. P.; Tsentalovich, Y. P.; Yurkovskaya, A. V.;
Sagdeev, R. Z. J. Phys. Chem. 1996, 100, 4448.
25. BzN, from decarboxylation, is also present in small yields.a,b
Since k1 occurs in parallel with lysis (kc), the extent of decarboxyl-
ation does not in¯uence the ratios of the relative yields of the
photoproducts derived from the radical pairs. (a) Finnegan, R.
A.; Knutson, D. J. Am Chem. Soc. 1967, 89, 1971. (b) Finnegan,
R. A.; Knutson, D. Chem. Ind. 1965, 1837.
5. Cui, C.; Weiss, R. G. J. Am. Chem. Soc. 1993, 115, 9820.
6. (a) Griller, D.; Ingold, K. U. Acc. Chem. Res. 1980, 13, 317.
(b) Pincock, J. A. Acc. Chem. Res. 1997, 30, 43.
7. (a) Nevill, S. M.; Pincock, J. A. Can. J. Chem. 1997, 75, 232.
(b) Horner, J. H.; Tanaka, N.; Newcomb, M. J. Am. Chem. Soc.
1998, 120, 10379 and refs cited therein.
26. Jent, F.; Paul, H.; Roduner, E.; Heming, M.; Fischer, H. Int. J.
Chem. Kinet. 1986, 18, 1113.
27. The relaxation times of occupied sites in polyole®ns are dif®-
cult to estimate because the size and shape of each guest will
in¯uence the chain segments constituting its host cage differently.
However, the NMR determined correlation time of C±H dipolar
interactions in the amorphous regions of polyethylenea and poly-
propyleneb are #50 ns. The correlation time of pyrene, which is
expected to disturb its cage environment much more than
molecules of 1, is ca. two order of magnitude shorter than that of
its host, an ethylene±propylene rubber.a (a) Tai, Y.; Okazaki, M.;
Toriyami, K. J. Chem. Soc., Faraday Trans. 1992, 88, 23.
(b) Tanaka, H.; Inoue, Y. Eur. Polym. J. 1993, 29, 569.
28. Gu, W.; Warrier, M.; Schoon, B.; Ramamurthy, V.; Weiss,
R. G. Langmuir, accepted for publication.
8. (a) Martin-Esker, A. A.; Johnson, C. C.; Horner, J. H.;
Newcomb, M. J. Am. Chem. Soc. 1994, 116, 9174. (b) Newcomb,
M.; Manek, M. B.; Glenn, A. G. J. Am. Chem. Soc. 1991, 113, 949.
9. See for instance: (a) Bowry, V. W.; Ingold, K. U. J. Am. Chem.
Soc. 1991, 113, 5699. (b) Liu, K. E.; Johnson, C. C.; Newcomb,
M.; Lippard, S. J. J. Am. Chem. Soc. 1993, 115, 939. (c) DeCosta,
D. P.; Pincock, J. A. J. Am. Chem. Soc. 1993, 115, 2180.
(d) Nagahara, K.; Ryu, I.; Kambe, N.; Komatsu, M.; Sonoda, N.
J. Org. Chem. 1995, 60, 7384.
10. Nakagaki, R.; Hiramatsu, M.; Watanabe, T.; Tanimoto, Y.
J. Phys. Chem. 1985, 89, 3222.
11. A different approach by Garcia-Garibay and coworkersa
employs photoreactions in neat crystalline phases. It has the advan-
tage that molecular conformations are known with greater certainty
than in viscous media, but it has the disadvantage that the range of
motions available to the reactive species is severely limited. Also,
the use of precursors to triplet radical pairs, to time much slower
events than the ones of interest here, is well-established.b,c (a) Choi,
T.; Peterfy, K.; Khan, S. I.; Garcia-Gariby, M. A. J. Am. Chem.
Soc. 1996, 118, 12477. (b) Hrovat, D. A; Liu, J. H.; Turro, N. J.;
Weiss, R. G. J. Am. Chem. Soc. 1984, 106, 5291. (c) Cozens, F. L.;
Scaiano, J. C. J. Am. Chem. Soc. 1993, 115, 5204.
29. Tsentalovich, Y. P.; Fischer, H. J. Chem. Soc., Perkin Trans. 2
1994, 729.
30. Braun, W.; Rajbenbach, L.; Eirich, F. R. J. Phys. Chem. 1962,
66, 1591.
31. (a) Michaels, A. S.; Bixler, H. J. J. Polym. Sci. 1961, 50, 413.
(b) Birks, J. B. In Organic Molecular Photophysics; Birks, J. B.,
Ed.; Wiley: New York, 1973; Vol. 1, p 403.
32. (a) Phillips, P. J. Chem. Rev. 1990, 90, 425. (b) Jang, Y. T.;
Phillips, P. J.; Thulstrup, E. W. Chem. Phys. Lett. 1982, 93, 66.
(c) Meirovitch, E. J. Phys. Chem. 1984, 88, 2629. (d) Naciri, J.;
Weiss, R. G. Macromolecules 1989, 22, 3928. (e) He, Z;
Hammond, G. S.; Weiss, R. G. Macromolecules 1992, 25, 1568.
(f) Jenkins, R. M.; Hammond, G. S.; Weiss, R. G. J. Phys. Chem.
1992, 96, 496.
12. Gu, W.; Warrier, M.; Ramamurthy, V.; Weiss, R. G. J. Am.
Chem. Soc. 1999, 121, 9467.
13. Turro, N. J.; Gould, I. R.; Baretz, B. H. J. Phys. Chem. 1983,
87, 531.
14. Zimerman, O. E.; Cui, C.; Wang, X.; Atvars, T.; Weiss, R. G.
Polymer 1998, 39, 1177.
33. (a) Dixon, W. T.; Foster, W. E. J.; Murphy, D. J. Chem. Soc.,
Perkin II 1973, 15, 2124. (b) Karplus, M.; Fraenkel, G. K. J. Chem.
Phys. 1961, 35, 1312.
15. (a) Uedono, A.; Kawano, T.; Tanigawa, S.; Ban, M.; Kyoto,
M.; Uozumi, T. J. Polym. Sci. B: Polym. Phys. 1997, 35, 1601 and
references cited therein. (b) Bu, H.; Cheng, S. Z. D.; Wunderlich,
B. Makromol. Chem. Rapid Commun. 1988, 9, 75. (c) Brandrup, J.;
34. Bondi, A. J. Phys. Chem. 1964, 68, 441.
35. (a) Jean, Y. C.; Deng, Q. J. Polym. Sci. B, Polym. Phys. 1992,