Abstract.
Intramolecular electron spin exchange, as a function of temperature and the solvent viscosity, polarity and relaxation properties of the solvent molecules, has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two long-chain flexible nitroxide biradicals existing in fluid solutions in three spectroscopically different spatial conformations. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. Spin exchange in two biradicals dissolved in five different alcohols was compared with that in a nonpolar solvent (toluene), polar protic (water) and aprotic (acetonitrile), and with thermodynamic characteristics of the solvents. Distinct correlations were found between macroscopic (solvent viscosity, polarity) and microscopic (solvent longitudinal relaxation time) characteristics of solvents, and thermodynamic parameters of the intramolecular conformational transitions.
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Kokorin, A.I., Tran, V.A., Rasmussen, K., Grampp, G.: Appl. Magn. Reson. 30, 40 (2006)
Buchachenko, A.L., Wasserman, A.M.: Stabil'nye Radikaly. Khimiya, Moscow (1973)
Parmon, V.N., Kokorin, A.I., Zhidomirov, G.M.: Zh. Strukt. Khim. 18, 104 (1977)
Parmon, V.N., Kokorin, A.I., Zhidomirov, G.M.: Stabil'nye Biradikaly. Nauka, Moscow (1980)
Grigor'ev, I.A., Dikanov, S.A., in: Volodarsky, L.B. (ed.) Imidazoline Nitroxides: Synthesis, Properties, Applications, vol. 1, pp. 77–150. CRC Press, Boca Raton, Fla. (1988)
Parmon, V.N., Kokorin, A.I., Zhidomirov, G.M., Zamaraev, K.I.: Mol. Phys. 30, 695 (1975)
Kozlov, S.V., Kokorin, A.I., Shapiro, A.B., Rozantsev, E.G.: Vysokomol. Soedin. Ser. B 23, 323 (1981)
Dikanov, S.A., Shchukin, G.I., Grigor'ev, I.A., Rukin, S.I., Volodarsky, L.B.: Izv. Akad. Nauk SSSR Ser. Khim. 3, 565 (1985)
Sankarapandi, S., Rifkind, J.M., Manoharan, P.T.: Proc. Indian Acad. Sci. (Chem. Sci.) 106, 1329 (1994)
Sankarapandi, S., Sukumar, M., Balaram, P., Manoharan, P.T.: Biochem. Biophys. Res. Commun. 213, 439 (1995)
Shapiro, A.B., Baimagambetov, K., Goldfield, M.G., Rozantsev, E.G.: Zh. Org. Khim. 8, 2263 (1972)
Rozantsev, E.G.: Free Nitroxyl Radicals. Plenum, New York (1970)
Rozantsev, E.G., Suskina, V.I.: Izv. Akad. Nauk SSSR Ser. Khim. 9, 2148 (1968)
Shapiro, A.B., Suskina, V.I., Fedorova, V.V., Rozantsev, E.G.: Izv. Akad. Nauk SSSR Ser. Khim. 4, 694 (1970)
Riddick, J.A., Bunger, W.B., Sakano, K.T.: Organic Solvents: Physical Chemistry and Methods of Purification. Techniques of Chemistry, vol. 2. Wiley, New York (1986)
Molin, Yu.N., Salikhov, K.M., Zamaraev, K.I.: Spin Exchange. Springer, Berlin (1980)
Marcus, Y.: The Properties of Solvents. Wiley, Chichester (1998)
Barthel, J., Buchner, R., Münsterer, M.: Dielectric Properties of Nonaqueous Solutions. Electrolyte Data Collection, part 2a. Chemistry Data Series, vol. 12. Dechema, Frankfurt am Main (1996)
Patil, S.P., Chaudhari, A.S., Lokhande, M.P., Lande, M.K., Shankarwar, A.G., Helambe, S.N., Arbad, B.R., Mehrotra, S.C.: J. Chem. Eng. Data 44, 875–878 (1999)
Garg, S.K., Smyth, C.P.: J. Chem. Phys. 46, 373–378 (1967)
Asaki, M.L.T., Redondo, A., Zawodzinski, T.A., Taylor, A.J.: J. Chem. Phys. 116, 10377–10385 (2002)
Buchner, R., Barthel, J., Stauber, J.: J. Chem. Phys. Lett. 306, 57–63 (1999)
Gilmont, R.: Meas. Control 10, 36 (2002)
Grampp, G., Rasmussen, K., Kokorin, A.I.: Appl. Magn. Reson. 26, 245 (2004)
Gilmont, R.: Meas. Control 10, 36 (2002)
Karapetýants, M.Kh., Yen, K.-S.: Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 4, 580 (1961)
Reichard, C.: Chem. Rev. 94, 2319–2258 (1994)
Grampp, G., Rasmussen, K.: Phys. Chem. Chem. Phys. 4, 5546 (2002)
Fröhlich, H.: Theory of Dielectrics, 2nd edn. Oxford University Press, Oxford (1949)
Buchner, R., Barthel, J.: J. Mol. Liquids 63, 55–75 (1995)
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Authors' address: Van Anh Tran, Institute of Physical and Theoretical Chemistry, Graz University of Technology, Technikerstrasse 4, 8010 Graz, Austria
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Tran, V., Rasmussen, K., Grampp, G. et al. The Solvent Effect on Spin Exchange in Long-Chain Nitroxide Biradicals. Appl Magn Reson 32, 395–406 (2007). https://doi.org/10.1007/s00723-007-0018-z
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DOI: https://doi.org/10.1007/s00723-007-0018-z