| Автор | Yoshihara, Toshitada |
| Автор | Galievsky, Victor A. |
| Автор | Druzhinin, Sergey I. |
| Автор | Saha, Satyen |
| Автор | Zachariasse, Klaas A. |
| Дата выпуска | 2003 |
| dc.description | The excited state dipole moments μe(ICT) and μe(LE) of the dual fluorescent molecules N-phenylpyrrole (PP), N-(4-cyanophenyl)pyrrole (PP4C) and N-(3-cyanophenyl)pyrrole (PP3C) are determined from solvatochromic and thermochromic measurements. It is shown that the best results are obtained when the solvatochromic as well as the thermochromic analysis of the spectral shifts is made relative to 4-(dimethylamino)benzonitrile (DMABN) as the model compound. Direct thermochromic experiments with PP4C, PP3C and DMABN in diethyl ether lead to reasonable results, but unrealistically large dipole moments μe(ICT) are found for PP, PP4C, PP3C and DMABN in acetonitrile, ethyl cyanide and n-propyl cyanide. The μe(ICT) values obtained for the N-phenylpyrroles from the thermochromic analysis in these solvents relative to DMABN (17 D) do not depend on solvent polarity: 13 D for PP, 15 D for PP4C and PP3C. The spectral shifts for the LE emission of the N-phenylpyrroles and aminobenzonitriles are much smaller than those for the ICT fluorescence, resulting in relatively small values for μe(LE). With PP and N-(4-methylphenyl)pyrrole (PP4M) the problem arises that one of the two values calculated by solving the quadratic equation for μe(LE) in the solvatochromic and thermochromic analysis cannot be discarded on photophysical or molecular grounds, as is the case for the other molecules. The experimental data for μe(ICT) of PP and PP4C are compared with theoretical values calculated for coplanar (PICT) and perpendicular (TICT) conformations of the pyrrole and phenyl or cyanophenyl groups. The experimental ICT dipole moment of PP4C has a value in between the theoretical results for μe(PICT) and μe(TICT), whereas the data for PP tend to favour the TICT configuration. It appears that in the LE state of PP and PP4M a negative charge remains on the pyrrole moiety, whereas a charge reversal takes place for the LE state of PP3C and the ICT state of PP, PP4C and PP3C. |
| Формат | application.pdf |
| Издатель | Royal Society of Chemistry |
| Название | Singlet excited state dipole moments of dual fluorescent N-phenylpyrroles and 4-(dimethylamino)benzonitrile from solvatochromic and thermochromic spectral shiftsDedicated to Professor Jean Kossanyi on the occasion of his 70th birthday. |
| Тип | research-article |
| DOI | 10.1039/b211838f |
| Electronic ISSN | 1474-9092 |
| Print ISSN | 1474-905X |
| Журнал | Photochemical & Photobiological Sciences |
| Том | 2 |
| Первая страница | 342 |
| Последняя страница | 353 |
| Аффилиация | Yoshihara Toshitada; Max-Planck-Institut für biophysikalische Chemie, Spektroskopie und Photochemische Kinetik |
| Аффилиация | Galievsky Victor A.; Max-Planck-Institut für biophysikalische Chemie, Spektroskopie und Photochemische Kinetik |
| Аффилиация | Druzhinin Sergey I.; Max-Planck-Institut für biophysikalische Chemie, Spektroskopie und Photochemische Kinetik |
| Аффилиация | Saha Satyen; Max-Planck-Institut für biophysikalische Chemie, Spektroskopie und Photochemische Kinetik |
| Аффилиация | Zachariasse Klaas A.; Max-Planck-Institut für biophysikalische Chemie, Spektroskopie und Photochemische Kinetik |
| Выпуск | 3 |
| Библиографическая ссылка | W. Rettig, F. Marschner, Population of excited charge transfer states and molecular conformation in N-phenylpyrroles, Nouv. J. Chim., 1983, 7, 425, 431 |
| Библиографическая ссылка | W. Rettig, Charge separation in excited states of decoupled systems-TICT compounds and implications regarding the development of new laser dyes and the primary processes of vision and photosynthesis, Angew. Chem., Int. Ed. Engl., 1986, 25, 971, 988 |
| Библиографическая ссылка | W. Rettig, F. Marschner, Molecular conformation and biradicaloid charge transfer states in substituted N-phenylpyrroles, New. J. Chem., 1990, 14, 819, 824 |
| Библиографическая ссылка | K. A. Zachariasse, T. Yoshihara, S. I. Druzhinin, Picosecond and nanosecond fluorescence decays of 4-(dimethylamino)phenylacetylene in comparison with those of 4-(dimethylamino)benzonitrile. No evidence for intramolecular charge transfer and a nonfluorescing intramolecular charge transfer state, J. Phys. Chem. A, 2002, 106, 6325, 6333, J. Phys. Chem. A, 2002, 106, 8978 |
| Библиографическая ссылка | A. Sarkar, S. Chakravorti, N, N, Chem. Phys. Lett., 1995, 235, 195, 201 |
| Библиографическая ссылка | J. Manz, B. Proppe, B. Schmidt, Time-resolved dual fluorescence of 1-phenylpyrrole in acetonitrile: molecular dynamics simulations of solvent response to twisted intramolecular charge transfer, Phys. Chem. Chem. Phys., 2002, 4, 1876, 1881 |
| Библиографическая ссылка | C. Cornelissen-Gude, W. Rettig, Dual fluorescence and multiple charge transfer nature in derivatives of N-pyrrolobenzonitrile, J. Phys. Chem. A, 1998, 102, 7754, 7760 |
| Библиографическая ссылка | W. Rettig, Application of a simplified microstructural solvent interaction model to the solvatochromism of twisted intramolecular charge transfer, J. Mol. Struct., 1982, 84, 303, 327 |
| Библиографическая ссылка | C. Cazeau-Dubroca, A. Peirigua, S. Ait Lyazidi, G. Nouchi, Ph. Cazeau, R. Lapouyade, TICT fluorescence in rigid matrices: α-delayed fluorescence, Chem. Phys. Lett., 1986, 124, 110, 115 |
| Библиографическая ссылка | K. Okuyama, Y. Numata, S. Odawara, I. Suzuka, Electronic spectra of jet-cooled 1-phenylpyrrole: large amplitude torsional motion and twisted intramolecular charge-transfer phenomena, J. Chem. Phys., 1998, 109, 7185, 7195 |
| Библиографическая ссылка | L. Belau, Y. Haas, W. Rettig, Jet cooled spectra of pyrrolobenzene and of pyrrolobenzonitrile: the nature of the excited states, Chem. Phys. Lett., 2002, 364, 157, 163 |
| Библиографическая ссылка | H. Okamoto, M. Kinoshita, Picosecond infrared spectrum of 4-(pyrrol-1-yl)benzonitrile: structure of the excited charge-transfer states of donor-acceptor systems, J. Phys. Chem. A, 2002, 106, 3485, 3490 |
| Библиографическая ссылка | B. Proppe, M. Merchán, L. Serrano-Andrés, Theoretical study of the twisted intramolecular charge transfer in 1-phenylpyrrole, J. Phys. Chem. A, 2000, 104, 1608, 1616 |
| Библиографическая ссылка | A. B. J. Parusel, N, N, N, N, Phys. Chem. Chem. Phys., 2000, 2, 5545, 5552 |
| Библиографическая ссылка | S. Zilberg, Y. Haas, p, J. Phys. Chem. A, 2002, 106, 1, 11 |
| Библиографическая ссылка | K. A. Zachariasse, M. Grobys, Th. von der Haar, A. Hebecker, Yu. V. Il'ichev, Y.-B. Jiang, O. Morawski, W. Kühnle, Intramolecular charge transfer in the excited state. Kinetics and configurational changes, J. Photochem. Photobiol. A, 1996, 102, 59, 70 |
| Библиографическая ссылка | K. A. Zachariasse, The PICT model for dual fluorescence of aminobenzonitriles, Chem. Phys. Lett., 2000, 320, 8, 13 |
| Библиографическая ссылка | Z. R. Grabowski, K. Rotkiewicsz, A. Siemiarczuk, D. J. Cowley, W. Baumann, Twisted intramolecular charge transfer states (TICT). A new class of excited states with a full charge separation, Nouv. J. Chim., 1979, 3, 443, 454 |
| Библиографическая ссылка | K. A. Zachariasse, M. Grobys, E. Tauer, Absence of dual fluorescence with 4-(dimethylamino)phenylacetylene. A comparison between experimental results and theoretical predictions, Chem. Phys. Lett., 1997, 274, 372, 382 |
| Библиографическая ссылка | W. Schuddeboom, S. A. Jonker, J. M. Warman, U. Leinhos, W. Kühnle, K. A. Zachariasse, Excited-state dipole moments of dual fluorescent 4-(dialkylamino)benzonitriles. Influence of alkyl chain length and effective solvent polarity, J. Phys. Chem., 1992, 96, 10809, 10819 |
| Библиографическая ссылка | Yu. V. Il'ichev, W. Kühnle, K. A. Zachariasse, Photophysics of 4-dimethylamino-4â ²-cyanostilbene and 4-azetidinyl-4â ²-cyanostilbene. Time-resolved fluorescence and trans-cis photoisomerisation, Chem. Phys., 1996, 211, 441, 453 |
| Библиографическая ссылка | W. Baumann, H. Bischof, J.-C. Fröhling, C. Brittinger, W. Rettig, K. Rotkiewicz, Considerations on the dipole moment of molecules forming the twisted intramolecular charge transfer state, J. Photochem. Photobiol. A, 1992, 64, 49, 72 |
| Библиографическая ссылка | A. Heine, R. Herbst-Irmer, D. Stalke, W. Kühnle, K. A. Zachariasse, Structure and crystal packing of 4-aminobenzonitriles and 4-amino-3,5-dimethylbenzonitriles at various temperatures, Acta Crystallogr., Sect. B, 1994, 50, 363, 371 |
| Библиографическая ссылка | A. Demeter, S. Druzhinin, M. George, E. Haselbach, J.-L. Roulin, K. A. Zachariasse, Dual fluorescence and fast intramolecular charge transfer with 4-(diisopropylamino)benzonitrile in alkane solvents, Chem. Phys. Lett., 2000, 323, 351, 360 |
| Библиографическая ссылка | H. Beens, A. Weller, Characteristics of molecular complexes in the excited state, Acta Phys. Pol., 1968, 34, 593, 542 |
| Библиографическая ссылка | H. Lumbroso, D. M. Bertin, F. Marschner, A dipole moment study of gradually hindered N-phenylpyrroles, J. Mol. Struct., 1988, 178, 187, 200 |
| Библиографическая ссылка | M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, General atomic and molecular electronic-structure system (Gamess), J. Comput. Chem., 1993, 14, 1347, 1363 |
| Библиографическая ссылка | P. Suppan, Temperature effects in solvatochromic shifts, J. Chem. Soc., Faraday Trans. 2, 1981, 77, 1553, 1562 |
| Библиографическая ссылка | P. Suppan, Thermochromic shifts of the fluorescence spectra of 4-N,N-dimethylaminobenzonitrile in solution, J. Lumin., 1985, 33, 29, 32 |
| Библиографическая ссылка | T. Hagan, D. Pilloud, P. Suppan, Thermochromic shifts of some molecular and exciplex fluorescence spectra, Chem. Phys. Lett., 1987, 139, 499, 502 |
| Библиографическая ссылка | P. Suppan, Solvatochromic shifts: the influence of the medium on the energy of electronic states, J. Photochem. Photobiol. A, 1990, 50, 293, 330 |
| Библиографическая ссылка | A. Kawski, W. Kolakowski, à ber die Temperaturabhängigkeit der Absorptions- und Fluoreszenzspektren von 4-Aminophthalimid, Acta Phys. Pol., 1966, 29, 177, 186 |
| Библиографическая ссылка | I. Gryczynski, A. Kawski, Temperaturabhängigkeit der statischen Dielektrizitätskonstante und des optischen Brechungsindexes von Flüssigkeiten, Z. Naturforsch., 1975, 30A, 287, 291 |
| Библиографическая ссылка | W. Rettig, D. Braun, P. Suppan, E. Vauthey, K. Rotkiewicsz, R. Luboradzki, K. SuwiÅ ska, Molecular conformation and excited-state dipole moments of di- and tetramethylaminobenzonitrile (DMABN and TMABN), J. Phys. Chem., 1993, 97, 13500, 13507 |
