Abstract
The ion pair structure of partially metallated poly(2-vinylfluorene) is studied by means of electronic absorption and fluorescence spectroscopy. The degree of metallation along the polymer chain influences the ion pair structure effectively. In the ground state the conversion of contact ion pairs into solvent-separated ion pairs along the polymer chain is depressed by electrostatic interaction between the ion pairs. The contact ion pairs with a bulky counter cation form aligned pendant fluorenide chromophores. In the excited state the steric effect of counter cation in the polymer chain hinders the rearrangement of the fluorenide chromophores after Franck-Condon transition and this effect is more remarkable with large counter cations. It is suggested that these polymer effects, electrostatic and steric effects, influence the conformation of the polymer chain. An intramolecular energy migration along the polymer chain is also studied.
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References
Department of Applied Chemistry, Faculty of Engineering, Iwate University, Ueda, Morioka, 020 Japan.
M. Szwarc, “Carbanions, Living Polymers, and Electron Transfer Processes”; Interscience Publishers: New York, 1968.
M. Szwarc, “Ions and Ion pairs in Organic Reactions, Vols. 1 and 2”; Wiley-Interscience: New York, 1972.
A. Streitwieser Jr, Acc. Chem. Res., 17, 353 (1984).
T. E. Hogen-Esch and J. Smid, J. Am. Chem. Soc., 87, 669 (1965); 88, 307 (1966); 90, 4654 (1968).
T. E. Hogen-Esch and J. Smid, J. Am. Chem. Soc., 88 318 (1966).
S. Nishi and M. Matsuda, J. Am. Chem. Soc., 101, 4632 (1979).
S. Nishi and M. Matsuda, Phosphorus and Sulfur, 16, 181 (1983).
H. R. Huson, Annual Reports on the Progress of Chemistry, London; The Royal Society of Chemistry, 76, 66, (1979).
A. Watanabe, M. Iino, and M. Matsuda, Polymer Preprints, Japan, 30, 200 (1981); 31, 649 (1982); 31, 423, (1982)
K. Wong, L. Ambroz, and J. Smid, J. Polymer Bull., 8, 411 (1982).
M. J. Plodinec and T. E. Hogen-Esch, J. Am. Chem. Soc., 96, 5262 (1974).
T. E. Hogen-Esch and J. Plodinec, J. Phys. Chem., 80, 1085, 1090 (1976).
T. E. Hogen-Esch and J. Plodinec, J. Am. Chem. Soc., 100, 7633, (1978).
A. Watanabe and M. Matsuda, British Polym. J., Part 1, in press.
A. Watanabe and M. Matsuda, Part 2, to be published.
A. Watanabe and M. Matsuda, Part 3, to be published.
M. Minabe, M. Yoshida, M. Fujimoto, and K. J. Suzuki, J. Org. Chem., 41, 1935 (1976).
E. Gipstein, W. A. Hewett, and O. U. Need, J. Polym. Sci. Part B, 9, 671 (1971).
H. C. Wang, G. Levin, and M. Szwarc, J. Am. Chem. Soc., 100, 6137 (1978).
G. C. Greenacre and R. N. Young, J. Chem. Soc. Perkin II, 874 (1976).
H. M. Parkes and R. N. Young, J. Chem. Soc. Perkin II, 1137, (1980).
A. Persoons and M. Van Beylen, Pure and Applied Chem., 51, 887, (1979).
M. Kasha, Radiation Res., 20, 55 (1963).
A. S. Davydov, “Theory of Molecular Excitons”; New York, 1962.
M. J. Turro, “Modern Molecular Photochemistry”; Benjamin: California, 1978.
H. W. Vos, C. MacLean, and N. H. Velthorst, J. Chem. Soc. Faraday II, 72, 63 (1976).
J. B. Birks, “Photophysics of Aromatic Molecules”; Interscience: New York, 1970.
F. Z. Schneider, Naturforsch, 24, 863, 1969.
C. A. G. Brooks and K. M. C. Davis, J. Chem. Soc. Perkin II, 1649 (1972).
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© 1987 Elsevier Science Publishing Co., Inc.
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Matsuda, M., Watanabe, A. (1987). Ion Pair Structure and Photochemistry of Partially Metallated Poly(2-Vinylfluorene) in Solution. In: Hogen-Esch, T.E., Smid, J. (eds) Recent Advances in Anionic Polymerization. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3175-6_5
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DOI: https://doi.org/10.1007/978-94-009-3175-6_5
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-010-7924-2
Online ISBN: 978-94-009-3175-6
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