Effective polarity of frozen solvent glasses in the vicinity of dipolar solutes

Journal of the American Chemical Society

Volumn 120, Issue 16, 1998, Pages 3988-3992

  Bublitz, Gerold U ^a   Boxer, Steven G ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CHEMICAL STRUCTURE; DIPOLE; ELECTRON TRANSPORT; MOLECULAR INTERACTION; MOLECULAR MODEL; SOLVATION;

EID: 0032577009     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja971665c     Document Type: Article

References (43)

1. Reichardt, C. Angew. Chem., Int. Ed. Engl. 1965, 4, 29-40.
2. Liptay, W. Z. Naturforsch. 1965, 20a, 1441-1471.
3. Reichardt, C.; Dimroth, K. Fortschr. Chem. Forsch. 1968, 11, 1-73.
4. Suppan, P. J. Photochem. Photobiol. A 1990, 50, 293-330.
5. Marcus, Y. Chem. Soc. Rev. 1993, 409-416.
6. Reichardt, C. Solvents and Solvent Effects in Organic Chemistry, 2nd ed.; VCH: Weinheim, 1988, and references therein.
7. Reichardt, C. Chem. Rev. (Washington, D.C.) 1994, 94, 2319-2358.
8. Dimroth, K.; Reichardt, C.; Schweig, A. Justus Liebigs Ann. Chem. 1963, 669, 95-105.
9. Kawski, A.; Kolakowski, W. Acta Phys. Pol. 1966, 29, 177-186.
10. Reichardt, C.; Harbusch, E.; Müller, R. In Advances in Solution Chemistry; Bertini, I., Lunazzi, L., Dei, A., Eds.; Plenum: New York, 1981; pp 275-293.
11. Suppan, P.; Tsiamis, C. J. Chem. Soc., Faraday Trans. 2 1981, 77, 1553-1562.
12. Hagan, T.; Pilloud, D.; Suppan, P. Chem. Phys. Lett. 1987, 139, 499-502.
13. Ghoneim, N.; Rohner, Y.; Suppan, P. Faraday Discuss. Chem. Soc. 1988, 86, 295-308.
14. Linert, W.; Jameson, R. F. J. Chem. Soc., Perkin Trans. 2 1993, 1415-1421.
15. Streck, C.; Richert, R. Ber. Bunsen-Ges. Phys. Chem. 1994, 98, 619-625.
16. The only other investigation (ref 13) of solvent polarity in rigid solvent matrixes we are aware of did not address this question. In fact, the authors of this study assumed a priori that a liquid solvent and a frozen glass will have an identical distribution of solvent molecules around the solute and thus attributed the observed increase in polarity exclusively to variations in the solvent dielectric constant.
17. Bublitz, G. U.; Ortiz, R.; Runser, C.; Fort, A.; Barzoukas, M.; Marder, S. R.; Boxer, S. G. J. Am. Chem. Soc. 1997, 119, 2311-2312.
18. Bublitz, G. U.; Ortiz, R.; Marder, S. R.; Boxer, S. G. J. Am. Chem. Soc. 1997, 119, 3365-3376.
19. MCH = methylcyclohexane; 2-MeTHF = 2-methyltetrahydrofuran; EtOH = ethanol.
20. THF = tetrahydrofuran; DMF = dimethylformamide; DMSO = dimethyl sulfoxide.
21. Reichardt, C.; Harbusch-Görnert, E. Liebigs Ann. Chem. 1983, 721-743.
22. This is clearly expected for molecules with a positive change in polarizability, Δα, between ground state and excited state, but has also been proposed to be generally true. See ref 2.
23. Dähne, S.; Leupold, D.; Nikolajewski, H.-E.; Radeglia, R. Z. Naturforsch. 1965, 20b, 1006-1007.
24. Radeglia, R.; Dähne, S. J. Mol. Struct. 1970, 5, 399-411.
25. Radeglia, R.; Engelhardt, G.; Lippmaa, E.; Pehk, T.; Nolte, K.-D.; Dähne, S. Org. Magn. Reson. 1972, 4, 571-576.
26. Baumann, W. Z. Naturforsch. 1983, 38a, 995-1002.
27. Blanchard-Desce, M.; Wortmann, R.; Lebus, S.; Lehn, J.-M.; Krämer, P. Chem. Phys. Lett. 1995, 243, 526-532.
28. Blanchard-Desce, M.; Alain, V.; Midrier, L.; Wortmann, R.; Lebus, S.; Glania, C.; Krämer, P.; Fort, A.; Muller, J.; Barzoukas, M. J. Photochem. Photobiol. A 1997, 105, 115-121.
29. -1 difference might be caused by the increase of dispersion forces due to this contraction.
30. Kohler, B. E.; Woehl, J. C. J. Chem. Phys. 1995, 102, 7773-7781.
31. Orrit, M.; Bernard, J.; Zumbusch, A.; Personov, R. I. Chem. Phys. Lett. 1992, 196, 595-600.
32. Mayer, E. J. Appl. Phys. 1985, 58, 663-667.
33. Oh, D.; Boxer, S. G. J. Am. Chem. Soc. 1989, 111, 1130-1131.
34. Oh, D. H., Boxer, S. G. J. Am. Chem. Soc. 1990, 112, 8161-8162.
35. Oh, D. H.; Sano, M.; Boxer, S. G. J. Am. Chem. Soc. 1991, 113, 6880-6890.
36. Shin, Y. K.; Brunschwig, B. S.; Creutz, C.; Sutin, N. J. Am. Chem. Soc. 1995, 117, 8668-8669.
37. Shin, Y. K.; Brunschwig, B. S.; Creutz, C.; Sutin, N. J. Phys. Chem. 1996, 100, 8157-8169.
38. Karki, L.; Lu, H. P.; Hupp, J. T. J. Phys. Chem. 1996, 100, 15637-15639.
39. Böttcher, C. J. F. Theory of Electric Polarization; 2nd ed.; Elsevier: Amsterdam, 1973; Vol. 1.
40. Miller, J. R.; Peeples, J. A.; Schmitt, M. J.; Closs, G. L. J. Am. Chem. Soc. 1982, 104, 6488-6493.
41. Gaines, G. L., III.; O'Neil, M. P.; Svec, W. A.; Niemczyk, M. P.; Wasielewski, M. R. J. Am. Chem. Soc. 1991, 113, 719-721.
42. Stowell, M. H. B.; McPhillips, T. M.; Rees, D. C.; Soltis, S. M.; Abresch, E.; Feher, G. Science 1997, 276, 812-816.
43. Steffen, M. A.; Lao, K.; Boxer, S. G. Science 1994, 264, 810-816.