Abstract
Highly polar excited molecular states relax in solutions to the “nonspectroscopic” supramolecular excited states comprising both the solute and the solvent cage. Final equilibrium geometry usually differs much from that in the ground state (e.g., highly polar exciplexes). In the case of singly bonded donor (D) — acceptor (A) molecules, the formation and structure of the “twisted” intramolecular charge-transfer (T.I.C.T.) excited states is proved, i.a., by means of the model compounds and picosecond absorption spectra in the excited states. The fluorescence emission from the T.I.C.T. states (and probably also from other highly polar exciplexes) is shown to be the radiative electron transfer. The latter is completing the set of processes which characterize the inverted Marcus region. Comparison of the radiative and nonradiative electron transfer processes offers a challenge to further research.
Dedicated to Professor Albert weller — who not only discovered the excited state electron transfer Processes, but also recognized their beauty — on his 65th birthday
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References
A. Weller, in The Exciplex (M. Gordon and W. R. Ware, eds., Academic Press, New York 1975) p.23.
S. Nagakura, in Excited States, vol.2 (E. C. Lim, ed., Academic Press, New York 1975) p.321.
H. Beens and A. Weller, in Organic Molecular Photophysics, vol.2 (J. B. Birks, ed., J. Wiley & Sons, London 1975) p.159.
N. Mataga and M. Ottolenghi, in Molecular Associations, vol.2 (R. Foster, ed., Academic Press, London 1979) p.l.
N. Mataga, T. Okada, H. Masuhara, N. Nakashima, Y. Sakata and S. Misumi, J. Lumin. 12/13 (1976) 159;
S. Masaki, T. Okada, N. Mataga, Y. Sakata and S. Misumi, Bull. Chem. Soc. Japan 49 (1976) 1277.
H. Knibbe, K. Röllig, F. P. Schäfer and A. Weller, J. Chem. Phys. 47 (1967) 1184.
E. Lippert, W. Lllder and H. Boos, in Advances in Molecular Spectroscopy (A. Mangini, ed., Pergamon Press, Oxford 1962) p.443.
K. Rotkiewicz, K. H. Grellmann and Z. R. Grabowski, Chem. Phys. Lett. 19 (1973) 315.
Z. R. Grabowski, K. Rotkiewicz, A. Siemiarczuk, D. J. Cowley and W. Baumann, Nouv. J. Chim. 3 (1979) 443.
W. Rettig, Angew. Chem. Int. Ed. Engl. 25 (1986) 971.
Z. R. Grabowski, Acta Phys. Polon. (U987) in press.
Z. R. Grabowski, J. Dobkowski and W. Kllhnle, J. Molec. Structure 114 (1984) 93.
J. Dobkowski, Z. R. Grabowski, E. Heumann, D. Khechinashvili, B. Kozankiewicz, W. Kllhnle and J. Sepiol, Proc. Internat. Symposium on Molecular Luminescence and Photophysics (Inst, of Physics, N. Copernicus Univ., Tor 1986) p.81.
E. Lippert, W. Rettig, V. Bonaciè-Koutecky, F. Heisel and J. A. Miehé, in Adv. in Chem. Physics, in press.
J. Lipski, H. Chojnacki, Z. R. Grabowski and K. Rotkiewicz, Chem. Phys. Lett. 70 (1980) 449.
W. Rettig, J. Phys. Chem. 86 (1982) 1970.
W. Baumann, in Meeting on Photoinduced Electron Transfer (Kyoto 1985) p.28.
R. J. Visser and C. A. G. O. Varma, J.C.S. Faraday Trans. II 76 (1980) 453.
R. J. Visser, C. A. G. O. Varma, J. Konijnenberg and P. Bergwerf, ibidem 79 (1983) 347.
T. Okada, N. Mataga and W. Baumann, J. Phys. Chem. 91 (1987) 760.
B. Chutny and A. J. Swallow, Trans. Faraday Soc. 66 (1970) 2847.
C. Rullière, Z. R. Grabowski and J. Dobkowski, Chem. Phys. Lett. in press.
T. Shida, S. Iwata and M. Imamura, J. Phys. Chem. 78 (1974) 741.
R. Potashnik, C. R. Goldschmidt, M. Ottolenghi and A. Weller, J. Chem. Phys. 55 (1971) 5344.
M. Vogel and W. Rettig, Ber. Bunsenges. Phys. Chem. 89 (1985) 962.
J. Ulstrup and J. Jortner, J. Chem. Phys. 63 (1975) 4358.
D. Rehm and A. Weller, Ber. Bunsenges. Phys. Chem. 73 (1969) 834.
J. R. Miller, L. T. Calcaterra and G. L. Closs, J. Am. Chem. Soc. 106 (1984) 3047.
M. R. Wasielewski and M. P. Niemczyk, Ibidem, 5043.
N. S. Hush, M. N. Paddon-Row, E. Cotsaris, H. Oevering, J. W. Verhoeven and M. Heppener, Chem. Phys. Lett. 117 (1985) 8.
J. R. Miller, J. V. Beitz and R. K. Huddieston, J. Am. Chem. Soc. 106 (1984) 5057.
M. R. Wasielewski, M. P. Niemczyk, W. A. Svec and E. B. Pewitt, ibidem 107 (1985) 1080.
T. Kakitani and N. Mataga, Chem. Phys. 93 (1985) 381; J. Phys. Chem. 90 (1986) 993.
H. Rau, Pure & Appl. Chem., in press.
T. Kakitani and N. Mataga, J. Phys. Chem. 89 (1985) 8.
R. A. Marcus, J. Chem. Phys. 43 (1965) 2654.
Z. R. Grabowski, Electrochim. Acta 13 (1968) 1218.
N. S. Hush, ibidem 1005.
V. G. Levich, in Adv. in Electrochem. and Electrochem. Eng. vol.4 (P. Delahay, ed., Interscience Publ., New York 1966) p.249.
Z. R. Grabowski, K. Rotkiewicz, W. Rubaszewska and E. Kirkor-Kamska, Acta Phys. Polon. A 54 (1978) 767.
A. Siemiarczuk, J. Koput and A. Pohorille, Z. Naturforsch. 37 a (1982) 598.
J. W. Verhoeven, Pure & Appl. Chem. 58 (1986) 1285.
Z. R. Grabowski and J. Dobkowski, ibidem 55 (1983) 245.
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Grabowski, Z.R. (1987). Molecular Structure in the Electron — Localized Excited States and the Radiative Electron Transfer. In: Balzani, V. (eds) Supramolecular Photochemistry. NATO ASI Series, vol 214. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3979-0_20
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DOI: https://doi.org/10.1007/978-94-009-3979-0_20
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