Dual emission from a family of conjugated dinuclear RuII complexes

Journal of the American Chemical Society

Volumn 127, Issue 12, 2005, Pages 4190-4192

  Glazer, Edith C ^a   Magde, Douglas ^a   Tor, Yitzhak ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIMER; RUBIDIUM;

ARTICLE; COMPLEX FORMATION; CONJUGATION; DUAL EMISSION; LUMINESCENCE; METAL BINDING; PHOTOSENSITIZATION; PHOTOSYNTHESIS; STEADY STATE; STRUCTURE ACTIVITY RELATION; ULTRAVIOLET SPECTROSCOPY;

EID: 16244407376     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0440304     Document Type: Article

References (37)

1. (a) Meyer, T. J. Acc. Chem. Res. 1989, 22, 163-170.
2. (b) Kurreck, H.; Huber, M. Angew. Chem., Int. Ed. Engl. 1995, 34, 849-866.
3. (c) Harriman, A.; Sauvage, J.-P. Chem. Soc. Rev. 1996, 25, 41-48.
4. (d) Harriman, A.; Ziessel, R. Chem Commun. 1996, 1707-1716.
5. (a) Juris, A.; Balzani, V.; Barigelletti, F.; Campagna, S.; Belser, P.; Von Zelewsky, A. Coord. Chem. Rev. 1988, 84, 85-277.
6. (b) Sauvage, J.-P.; Collin, J.-P.; Chambron, J.-C.; Guillerez, S.; Coudret, C.; Balzani, V.; Barigelletti, F.; De Cola L.; Flamigni, L. Chem. Rev. 1994, 94, 993-1019.
7. (c) Balzani, V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Chem. Rev. 1996, 96, 659-833 and references therein.
8. (a) Balzani, V.; Scandola, F. Supramolecular Photochemistry; Ellis Horwood: New York, 1991.
9. (b) Kalyanasundaram, K. Photochemistry of Polypyridine and Porphyrin Complexes, 1st ed.; Academic Press Limited: San Diego, 1992.
10. (c) Kalyanasundaram, K.; Grätzel, M. Coord. Chem. Rev. 1998, 77, 347-414.
11. II complexes, see ref 2a.
12. Kasha, M. Faraday Soc. Discuss. 1950, 9, 14-19.
13. 1MLCT state. See Browne, W, R.; Coates, C. G.; Brady, C.; Matousek, P.; Towrie, M.; Botchway, S. W.; Parker, A. W.; Vos, J. G.; McGarvey, J. J. J. Am. Chem. Soc. 2003, 125, 1706-1707.
14. DeArmond, M. K.; Carlin, C. M. Coord. Chem. Rev. 1981, 36, 325-355.
15. (a) Blakley, R. L.; Myrick, M. L.; DeArmond, M. K. J. Am. Chem. Soc. 1986, 108, 7843-7844.
16. (b) Keyes, T. E.; O'Connor, C.; Vos, J. G. Chem. Commun. 1998, 889-890.
17. (c) Baba, A, I.; Shaw, J. R.; Simon, J. A.; Thummel, R. P.; Schmehl, R. H. Coord. Chem. Rev. 1998, 171, 43-59.
18. (d) Tyson, D. S.; Luman, C. R.; Zhou, X.; Castellano, F. N. Inorg. Chem. 2001, 40, 4063-4071.
19. (e) Song, L.; Feng, J.; Wang, X.; Yu, J.; Hou, Y.; Xie, P.; Zhang, B.; Xiang, J.; Ai, X.; Zhang, J. Inorg. Chem. 2003, 42, 3393-3395.
20. (a) Blakley, R. L.; DeArmond, M. K. J. Am. Chem. Soc. 1987, 109, 4895-4901.
21. (b) Taffarel, E.; Chirayil, S.; Kim, W. Y.; Thummel, R. P.; Schmehl, R. H. Inorg. Chem. 1996, 35, 2127-2131.
22. (c) Suzuki, T.; Kuchiyama, T.; Kishi, S.; Kaizaki, S.; Takagi, H.; Kato, M. Inorg. Chem. 2003, 42, 785-795.
23. Note the dinuclear complexes studied are a mixture of diastereoisomers.
24. See Supporting Information for additional experimental details.
25. Tzalis, D.; Tor, Y. Tetrahedron Lett. 1995, 34, 6017-6020.
26. The presence of two distinct transitions, while not uncommon in heteroleptic complexes, is somewhat surprising given the simple spectrum for isomer 2.
27. 2+ ion; the absorption spectra was red-shifted, as expected, but the longest wavelength absorption remained below 400 nm (see Figure S5).
28. II complexes exhibit diminished lifetimes associated with lower-energy emission, consistent with the energy gap law, enhanced lifetimes have been observed with highly conjugated ligands, which decrease distortion in the excited state. See Boyde, S.; Strouse, G. F.; Jones, W. E.; Meyer, T. J. J. Am. Chem. Soc. 1990, 112, 7395-7396.
29. Similar results were obtained for the time-resolved studies in other solvents; see Figure S2 for the emission decays of 3 in methylene chloride.
30. Quantum yields were measured according to the guidelines of Demas, J. N.; Crosby, G. A. J. Phys. Chem. 1971, 75, 991-1024.
31. This value is approximate due to the low quantum yield, and the fact that the two emissive states possess overlapping excitation spectra.
32. Dual emission of the "distinct orbital" type has been reported in coordination complexes that contain appended organic fluorophores, but are not true violations of Kasha's rule, as they are considered "composite molecules." See refs 8c-e and (a) Simon, J. A.; Curry, S. L.; Schmehl, R. H.; Schatz, T. R.; Piotrowiak, P.; Jin, X., Thummel, R. R. J. Am. Chem. Soc. 1997, 110122-11022.
33. (b) Tyson, D. S.; Henbest, K. B.; Bialecki, J.; Castellano, F. N. J. Phys. Chem. A 2001, 105, 8154-8161.
34. Yeh, A. T.; Shank, C. V.; McCusker, J. K. Science 2000, 289, 935-938.
35. Grosshenny, V.; Harriman, A.; Romero, F. M.; Ziessel, R. J. Phys. Chem. 1996, 100, 17472-17484.
36. The absence of additional emission features in these systems may be related to the flexibility of the bpy-linked systems. Dual emission results from avoidance of standard radiationless decay pathways, and studies on classical systems, such as biphenyl and 9,10-dihydrophenanrthrene, show that a reduction in radiationless decay occurs with increased structural rigidity. See Nijegorodov, N. I.; Downey, W. S. J. Phys. Chem. 1994, 98, 5639-5643.
37. Although there are no reports of dual emission from 4-substituted phenanthrolines in the literature, there is a mention of unpublished results that provided evidence for dual emission from a 4,7-substituted phenanthroline complex at low temperature. See Blakley, R. L.; Myrick, M. L.; DeArmond, M. K. J. Phys. Chem. 1990, 94, 4804-4809.