Artículo
Abstract:
The solvatochromism and thermochromism of 4-aminophthalimide and 4-amino-N-methylphthalimide were studied by absorption and steady state and time-resolved fluorescence emission in solvent mixtures of toluene-ethanol and toluene-acetonitrile in the temperature range 5-70 °C. The wavelengths of the maximum of absorption and of fluorescence emission shift to the red with the increase of the proportion of the polar component in the mixture. The greater affinity for the polar component of the mixture of the excited state compared to the ground state enhances preferential solvation, which is the origin of this red shift. On the other hand, a spectral shift to the blue is found upon temperature increase in solvent mixtures. This fact can be explained by considering that association of the polar component with the excited-state solute is exothermic and decreases with temperature. The appointed solvation change is attained by diffusion-controlled exchange of solvent molecules between the bulk and the solvation sphere. This process leads to a time-dependent emission spectrum in the nanosecond time domain. In this work a kinetic scheme is developed to describe this exchange and explain the time-dependent fluorescence emission spectra. The description is based on a Langmuir type association of the solvent molecules with the solute. The solvation equilibrium is attained by stepwise solvent exchange. The kinetic data and the spectral information are integrated in a thermodynamic cycle that can describe the solvation of excited and ground states at any solvent composition.
Registro:
| Documento: | Artículo |
| Título: | Dynamic solvation of aminophthalimides in solvent mixtures |
| Autor: | Wetzler, D.E.; Chesta, C.; Fernández-Prini, R.; Aramendía, P.F. |
| Filiación: | Departamento de QIAQF, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, CI428EHA Buenos Aires, Argentina Departamento de Química y Física, Universidad Nacional de Río Cuarto, 5800 Río Cuarto, Argentina Unidad de Actividad Química, CNEA, Libertador 8250, 1428 Buenos Aires, Argentina |
| Palabras clave: | Fluorescence emission shift; Diffusion; Fluorescence; Ground state; Solvents; Thermodynamics; Aromatic compounds |
| Año: | 2002 |
| Volumen: | 106 |
| Número: | 11 |
| Página de inicio: | 2390 |
| Página de fin: | 2400 |
| DOI: | http://dx.doi.org/10.1021/jp0118423 |
| Título revista: | Journal of Physical Chemistry A |
| Título revista abreviado: | J Phys Chem A |
| ISSN: | 10895639 |
| CODEN: | JPCAF |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10895639_v106_n11_p2390_Wetzler |
Referencias:
- Reichardt, C., (1994) Chem. Rev., 94, p. 2319
- Lakowicz, J.R., (1999) Principles of Fluorescence Spectroscopy, 2nd ed., , Kluwer Academic, Plenum Publishers: New York, Chapter 6
- Matyushov, D.M., Voth, G.A., (1999) J. Chem. Phys., 111, p. 3630
- Khajehpour, M., Kauffman, J.F., (2000) J. Phys. Chem. A, 104, p. 9512
- Marcus, Y., (1993) Chem. Soc. Rev., 22, p. 409
- Bosch, E., Rosés, M., (1992) J. Chem. Soc., Faraday Trans., 88, p. 3541
- Suppan, P., (1987) J. Chem. Soc., Faraday. Trans. 1, 83, p. 495
- Suppan, P., (1990) J. Photochem. Photobiol., A, 50, p. 293
- Mazurenko, Y.T., Bakshiev, N.K., (1970) Opt. Spectrosc., 28, p. 490
- Chapman, C.F., Fee, R.S., Maroncelli, M., (1995) J. Phys. Chem., 99, p. 4811
- Moore, R.A., Lee, J., Robinson, G.W., (1985) J. Phys. Chem., 89, p. 3648
- Bakhshiev, N.G., Mazurenko, Y.T., Piterskaya, I.V., (1966) Opt. Spectrosc., 21, p. 307
- Ware, W.R., Lee, S.K., Brant, G.J., Chow, P.P., (1971) J. Chem. Phys., 54, p. 4729
- Harju, T., Huizer, A.H., Varma, C.A.G.O., (1995) Chem. Phys., 200, p. 214
- Laitinen, E., Salonen, K., Harju, T., (1996) J. Chem. Phys., 105, p. 9771
- Soujanya, T., Krishna, T.S.R., Samanta, A., (1992) J. Phys. Chem., 96, p. 8544
- Saroja, G., Samanta, A., (1995) Chem. Phys. Lett., 246, p. 506
- Das, S., Datta, A., Bhattacharyya, K., (1997) J. Phys. Chem. A, 101, p. 3299
- Datta, A., Das, S., Mandal, D., Pal, K., Bhattacharyya, K., (1997) Langmuir, 13, p. 6922
- Yuan, D., Brown, R.G., (1997) J. Phys. Chem. A, 101, p. 3461
- Betts, T.A., Bright, F.V., (1990) Appl. Spectrosc., 44, p. 1203
- Rapp, W., Klingenberg, H.H., Lessing, H.E., (1971) Ber. Bunsen-Ges. Phys. Chem., 75, p. 883
- Lakowicz, J.R., (1999) Principles of Fluorescence Spectroscopy, 2nd ed., , Kluwer Academic, Plenum Publishers: New York, Chapter 7
- Marcus, Y., (1985) Ion Solvation, , John Willey and Sons Ltd.: Chichester, Great Britain, Chapter 6
- Cortés, J., Heitele, H., Jortner, J., (1994) J. Phys. Chem., 98, p. 2527
- Il'ichev, Y.V., Kühnle, W., Zachariasse, K.A., (1998) J. Phys. Chem., 102, p. 5670
- Calculations performed by Dr. Dario Estrin (INQUIMAE, Universidad de Buenos Aires) with DFT predict an interaction energy of -26 kJ/mol between one ethanol molecule and AMP; Turro, N.J., (1991) Modern Molecular Photochemistry, , Univ Science Books: Sausalito, CA, Chapter 9
- Tachiya, M., (1975) Chem. Phys. Lett., 33, p. 289
- Tachiya, M., (1982) J. Chem. Phys., 76, p. 340
- Flanagin, L.W., Balbuena, P.B., Johnston, K.P., Rossky, P.J., (1997) J. Phys. Chem. B., 101, p. 7998
- Vath, P., Zimmt, M.B., Matyushov, D.V., Voth, G.A., (1999) J. Phys. Chem. B, 103, p. 9130
- Soujanya, T., Fessenden, R.W., Samanta, A., (1996) J. Phys. Chem., 100, p. 3507
Citas:
---------- APA ----------
Wetzler, D.E., Chesta, C., Fernández-Prini, R. & Aramendía, P.F. (2002) . Dynamic solvation of aminophthalimides in solvent mixtures. Journal of Physical Chemistry A, 106(11), 2390-2400.http://dx.doi.org/10.1021/jp0118423
---------- CHICAGO ----------
Wetzler, D.E., Chesta, C., Fernández-Prini, R., Aramendía, P.F. "Dynamic solvation of aminophthalimides in solvent mixtures" . Journal of Physical Chemistry A 106, no. 11 (2002) : 2390-2400.http://dx.doi.org/10.1021/jp0118423
---------- MLA ----------
Wetzler, D.E., Chesta, C., Fernández-Prini, R., Aramendía, P.F. "Dynamic solvation of aminophthalimides in solvent mixtures" . Journal of Physical Chemistry A, vol. 106, no. 11, 2002, pp. 2390-2400.http://dx.doi.org/10.1021/jp0118423
---------- VANCOUVER ----------
Wetzler, D.E., Chesta, C., Fernández-Prini, R., Aramendía, P.F. Dynamic solvation of aminophthalimides in solvent mixtures. J Phys Chem A. 2002;106(11):2390-2400.http://dx.doi.org/10.1021/jp0118423
