Abstract
A series of C60 fullerene derivatives containing a nitroxide group has been photoexcited by short LASER pulses in the microwave cavity of a cw-EPR spectrometer. Strongly spin polarized signals have been observed, in glassy matrix as well as in liquid solution, for both the ground electronic state and the excited quartet state. In the quartet state the excitation resides in the fullerene part and the molecule constitutes a triplet-radical pair with the partner covalently linked. The absorptive or emissive character of the transitions is explained in terms of the mechanism of radicaltriplet interaction producing spin polarization. Opposite initial sign and polarization patterns are observed for molecules with different spacer between nitroxide and fullerene. The time evolution of the relevant sublevel populations is fitted by a kinetic model taking into account quartet decay constants, quartet and doublet spin-lattice relaxation rates and branching ratios.
Similar content being viewed by others
References
Salikhov K.M., Molin Yu.N., Sagdeev R.Z., Buchachenko A.L.: Spin Polarization and Magnetic Field Effects in Radical Reactions (Molin Y.N., ed.). Amsterdam: Elsevier 1984.
Muus L.M., Atkins P.W., McLauchlan K.A., Pedersen J.B. (eds.): Chemical Induced Magnetic Polarization. Dordrecht: Reidel 1977.
Adrian F.J.: J. Chem. Phys.54, 3918 (1971);ibid. Adrian F.J.: J. Chem. Phys.57, 5107 (1972)
Pedersen J.B., Freed J.H.: J. Chem. Phys.58, 2746 (1973);ibid. Pedersen J.B., Freed J.H.: J. Chem. Phys.59, 2869 (1973)
Atkins P.W., Gurd R.C., McLauchlan K.A., Simpson A.F.: Chem. Phys. Lett.8, 55 (1971)
Wong S.K., Huchinson D.A., Wan J.K.S.: J. Am. Chem. Soc.95, 622 (1973)
Atkins P.W., Evans G.T.: Mol. Phys.27, 1633 (1974)
Pedersen J., Freed J.H.: J. Chem. Phys.62, 1706 (1975)
Avdievich N.I., Forbes M.D.E.: J. Phys. Chem.100, 1993 (1996)
Dzuba S.A., Gast P., Hoff A.J.: Chem. Phys. Lett.236, 595 (1995)
Dzuba S.A., Bosch M.K., Hoff A.J.: Chem. Phys. Lett.248, 427 (1996)
Tang J., Thurnauer M.C., Norris J.R.: Chem. Phys. Lett.219, 283 (1994)
Kothe G., Weber S., Ohmes E., Thurnauer M.C., Norris J.R.: J. Phys. Chem.98, 2706 (1994)
Kawai A., Okutsu T., Obi K.: J. Phys. Chem.95, 9130 (1991)
Kawai A., Obi K.: J. Phys. Chem.95, 5701 (1992)
Corvaja C., Franco L., Pasimeni L., Toffoletti A., Montanari L.: Chem. Phys. Lett.210, 355 (1993)
Corvaja C., Franco L., Toffoletti A.: Appl. Magn. Reson.7, 257 (1994)
Corvaja C., Franco L., Pasimeni L., Toffoletti A.: J. Chem. Soc. Faraday Trans.90, 3267 (1994)
Blättler C., Jent F., Paul H.: Chem. Phys. Lett.166, 375 (1990)
Swemberg C.E., Geacintov N.E. in: Organic Molecular Photophysics (Birks J.B., ed.), vol. 1. New York: Wiley 1973
Arbogast J.W., Darmanyan A.P., Foote C.S., Rubin Y., Diederich F.N., Alvarez M.M., Anz S.J., Whetten R.L.: J. Phys. Chem.95, 11 (1991)
Anderson J.L., An Y.-Z., Rubin Y., Foote C.S.: J. Am. Chem. Soc.116, 9763 (1994)
Bennati M., Grupp A., Mehring M., Dinse K.P., Fink J.: Chem. Phys. Lett.200, 440 (1992)
Closs G.L., Gautman P., Zhang D., Krusic P.J., Hill S.A., Wasserman E.: J. Phys. Chem.96, 69243 (1992)
Levanon H., Meiklyar V., Michaeli A., Michaeli S., Regev A.: J. Phys. Chem.96, 6128 (1992)
Regev A., Gamliel D., Meiklyar V., Michaeli S., Levanon H.: J. Phys. Chem.97, 3671 (1993)
Gamliel D., Levanon H.: J. Chem. Phys.97, 7140 (1992)
Negri F., Orlandi G., Zerbetto F.: Chem. Phys. Lett.144, 31 (1988)
Surjan P.R., Uvardi L., Nemeth K.: J. Mol. Struct. (Theochem.)311, 55 (1994)
Agostini G., Corvaja C., Pasimeni L.: Chem Phys.202, 349 (1996)
Agostini G., Corvaja C., Maggini M., Pasimeni P., Prato M.: J. Phys. Chem.100, 13416 (1996)
Corvaja C., Maggini M., Prato M., Scorrano G., Venzin M.: J. Am. Chem. Soc.117, 8857 (1995)
Arena F., Bullo F., Conti F., Corvaja C., Maggini M., Prato M., Scorrano G.: J. Am. Chem. Soc.119, 789–795 (1997)
Maggini M., Scorrano G., Prato M.: J. Am. Chem. Soc.115, 9798 (1993)
Griffith O.H., Waggoner A.S.: Acc. Chem. Res.2, 17 (1969)
Furrer R., Fujara F., Lange C., Stehlik D., Vieth H.M., Vollman W.: Chem. Phys. Lett.75, 332 (1980)
Shushin A.I.: Z. Physik. Chem.182, 9 (1993)
Abragam A.: The Principles of Nuclear Magnetism. Oxford: Clarendon Press 1961.
Lemaire H., Levy B., Rassat A. in: La Structure Hyperfine des Atomes et des Molecules: Colloque du Centre National de la Recherche Scientifique. Paris 1966.
Kawakami T., Yamanaka S., Mori W., Yamaguchi K., Kajiwara A.: Chem. Phys. Lett.235, 414 (1995)
Luckhurst G.R.: in Spin Labeling, Theory and Applications: Biradicals as Spin Probes (Berliner L.J., ed.), chap. 4, pp. 133–181. New York: Academic Press 1976.
Schouler M.C., Decorps M., Genoud F.: Mol. Phys.6, 1671 (1976)
Musin R.N., Schastnev P.V.: Zh. Strukt. Khim.17, 419 (1976)
McConnell H.C.: J. Chem. Phys.39, 1910 (1963)
Koga N., Morokuma K.: Chem. Phys. Lett.196, 191 (1992)
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Corvaja, C., Maggini, M., Ruzzi, M. et al. Spin polarization in fullerene derivatives containing a nitroxide group. Observation of the intermediate photoexcited quartet state in radical triplet pair interaction. Appl. Magn. Reson. 12, 477–493 (1997). https://doi.org/10.1007/BF03164128
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF03164128