Electroabsorption Studies of Metal-to-Ligand Charge Transfer in Ru(phenanthroline)32+: Evidence for Intrinsic Charge Localization in the Initially Formed Excited State

Inorganic Chemistry

Volumn 36, Issue 15, 1997, Pages 3318-3321

  Karki, Laba ^a   Hupp, Joseph T ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000340911     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic961349j     Document Type: Article

References (28)

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2. For reviews, see: (a) Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin Complexes; Academic Press: New York, 1992. (b) Juris, A.; Belser, P.; von Zelewsky, A.; Barigelletti, P.; Balzani, V. Coord. Chem. Rev. 1988, 84, 85. (c) Meyer, T. J. Acc. Chem. Res. 1978, 11, 94. (d) Benasson, R.; Salet, C.; Balzani, V. J. Am. Chem. Soc. 1977, 98, 3722.
3. For reviews, see: (a) Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin Complexes; Academic Press: New York, 1992. (b) Juris, A.; Belser, P.; von Zelewsky, A.; Barigelletti, P.; Balzani, V. Coord. Chem. Rev. 1988, 84, 85. (c) Meyer, T. J. Acc. Chem. Res. 1978, 11, 94. (d) Benasson, R.; Salet, C.; Balzani, V. J. Am. Chem. Soc. 1977, 98, 3722.
4. For reviews, see: (a) Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin Complexes; Academic Press: New York, 1992. (b) Juris, A.; Belser, P.; von Zelewsky, A.; Barigelletti, P.; Balzani, V. Coord. Chem. Rev. 1988, 84, 85. (c) Meyer, T. J. Acc. Chem. Res. 1978, 11, 94. (d) Benasson, R.; Salet, C.; Balzani, V. J. Am. Chem. Soc. 1977, 98, 3722.
5. See, for example: (a) Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1979, 101, 4391. (b) Bradley, P. G.; Kress, N.; Hornberger, B. A.; Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1981, 103, 7441. (c) Oh, D. H.; Boxer, S. G. J. Am. Chem. Soc. 1989, 111, 1130.
6. See, for example: (a) Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1979, 101, 4391. (b) Bradley, P. G.; Kress, N.; Hornberger, B. A.; Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1981, 103, 7441. (c) Oh, D. H.; Boxer, S. G. J. Am. Chem. Soc. 1989, 111, 1130.
7. See, for example: (a) Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1979, 101, 4391. (b) Bradley, P. G.; Kress, N.; Hornberger, B. A.; Dallinger, R. F.; Woodruff, W. H. J. Am. Chem. Soc. 1981, 103, 7441. (c) Oh, D. H.; Boxer, S. G. J. Am. Chem. Soc. 1989, 111, 1130.
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10. Kober, Sullivan and Meyer (Inorg. Chem. 1984, 23, 2098) (See also: Brunschwig; et al. J. Phys. Chem. 1987, 91, 4714) conclude from solvatochromic studies that Δμ for MLCT excitation of 1 is 14 ± 6 D. From related studies of 2 (see Supporting Information) we obtain an estimated Δμ of 13 ± 5 D.
11. Kober, Sullivan and Meyer (Inorg. Chem. 1984, 23, 2098) (See also: Brunschwig; et al. J. Phys. Chem. 1987, 91, 4714) conclude from solvatochromic studies that Δμ for MLCT excitation of 1 is 14 ± 6 D. From related studies of 2 (see Supporting Information) we obtain an estimated Δμ of 13 ± 5 D.
12. Kober, E. M.; Meyer, T. J. Inorg. Chem. 1985, 24, 107.
13. (a) Kober, E. M.; Sullivan, B. P.; Meyer, T. J. J. Am. Chem. Soc. 1982, 104, 630.
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17. Liptay, W. In Excited States; Lim, E. C., Ed.; Academic Press: New York, 1974; Vol. 1, pp 129-229.
18. Boxer, S. G. In The Photosynthetic Reaction Center; Academic Press: New York. 1993; Vol II, pp 179-220.
19. s is the static dielectric constant of the glass or solvent. From glass dielectric data reported by Karki and Hupp (J. Am. Chem. Soc., in press) f is ∼1.3.
20. Mathies, R. A. Ph.D. Thesis, Cornell University, 1974.
21. (a) Liptay, W. Ber. Bunsen-Ges. Phys. Chem. 1976, 80, 207-217.
22. (b) Oh, D. H.; Sano, M.; Boxer, S. G. J. Am. Chem. Soc. 1991, 113, 6880.
23. Press, W. H.; Flannery, B. P.; Teukolsky, S. A.; Vetterling, W. T. In Numerical Recipes: The Art of Scientific Computing; Cambridge University Press: Cambridge, U.K., 1989.
24. Kober E. M.; Meyer, T. J. Inorg. Chem. 1982, 21, 3967.
25. 18 Nevertheless, the approximate agreement between the dipole parameters derived from the one-component versus three-component fit suggests that the numerical findings are robust with respect to the details of spectral deconvolution.
26. -1) are both ca. 5.5 ± 2 D.
27. For related examples, see: Coe, B. J.; Thompson, D. W.; Culertson, C. T.; Schoonover, J. R.; Meyer, T. J. Inorg. Chem. 1995, 34, 3385.
28. 2c.18