Singlet excited state dipole moments of dual fluorescent N-phenylpyrroles and 4-(dimethylamino)benzonitrile from solvatochromic and thermochromic spectral shifts
作者： Toshitada Yoshihara , Victor A. Galievsky , Sergey I. Druzhinin , Satyen Saha , Klaas A. Zachariasse
DOI: 10.1039/B211838F
关键词:
摘要: The excited state dipole moments μe(ICT) and μe(LE) of the dual fluorescent molecules N-phenylpyrrole (PP), N-(4-cyanophenyl)pyrrole (PP4C) N-(3-cyanophenyl)pyrrole (PP3C) are determined from solvatochromic thermochromic measurements. It is shown that best results obtained when as well analysis spectral shifts made relative to 4-(dimethylamino)benzonitrile (DMABN) model compound. Direct experiments with PP4C, PP3C DMABN in diethyl ether lead reasonable results, but unrealistically large found for PP, acetonitrile, ethyl cyanide n-propyl cyanide. values N-phenylpyrroles these solvents (17 D) do not depend on solvent polarity: 13 D 15 PP4C PP3C. LE emission aminobenzonitriles much smaller than those ICT fluorescence, resulting relatively small μe(LE). With PP N-(4-methylphenyl)pyrrole (PP4M) problem arises one two calculated by solving quadratic equation cannot be discarded photophysical or molecular grounds, case other molecules. experimental data compared theoretical coplanar (PICT) perpendicular (TICT) conformations pyrrole phenyl cyanophenyl groups. moment has a value between μe(PICT) μe(TICT), whereas tend favour TICT configuration. appears PP4M negative charge remains moiety, reversal takes place
rsc.org
mpg.de
sci-hub.se 参考文章(34)
Klaas A Zachariasse, The PICT model for dual fluorescence of aminobenzonitriles. Chemical Physics Letters. ,vol. 320, pp. 8- 13 ,(2000) , 10.1016/S0009-2614(00)00230-X
J. B. Birks, Photophysics of aromatic molecules Wiley-Interscience. ,(1970)
Thomas Hagan, Denis Pilloud, Paul Suppan, Thermochromic shifts of some molecular and exciplex fluorescence spectra Chemical Physics Letters. ,vol. 139, pp. 499- 502 ,(1987) , 10.1016/0009-2614(87)87330-X
Wolfram Baumann, H. Bischof, J.-C. Fröhling, C. Brittinger, Wolfgang Rettig, Krystyna Rotkiewicz, Considerations on the dipole moment of molecules forming the twisted intramolecular charge transfer state Journal of Photochemistry and Photobiology A: Chemistry. ,vol. 64, pp. 49- 72 ,(1992) , 10.1016/1010-6030(92)85093-A
Paul Suppan, Thermochromic shifts of the fluorescence spectra of 4-N,N-dimethylaminobenzonitrile in solution Journal of Luminescence. ,vol. 33, pp. 29- 32 ,(1985) , 10.1016/0022-2313(85)90026-2
C. Cazeau-Dubroca, A. Peirigua, S.Ait Lyazidi, G. Nouchi, Ph. Cazeau, R. Lapouyade, Tict fluorescence in rigid matrices: α-delayed fluorescence Chemical Physics Letters. ,vol. 124, pp. 110- 115 ,(1986) , 10.1016/0009-2614(86)85128-4
Hiromi Okamoto, Mariko Kinoshita, Picosecond Infrared Spectrum of 4-(Pyrrol-1-yl)benzonitrile: Structure of the Excited Charge-Transfer States of Donor-Acceptor Systems† Journal of Physical Chemistry A. ,vol. 106, pp. 3485- 3490 ,(2002) , 10.1021/JP0126098
Henri Lumbroso, Daniel Marcel Bertin, Freimut Marschner, A dipole moment study on gradually hindered N-phenylpyrroles Journal of Molecular Structure. ,vol. 178, pp. 187- 200 ,(1988) , 10.1016/0022-2860(88)85017-8
Klaas A. Zachariasse, Mauricio Grobys, Erich Tauer, Absence of dual fluorescence with 4-(dimethylamino) phenylacetylene. A comparison between experimental results and theoretical predictions Chemical Physics Letters. ,vol. 274, pp. 372- 382 ,(1997) , 10.1016/S0009-2614(97)00668-4
Paul Suppan, Chris Tsiamis, Temperature effects in solvatochromic shifts Journal of the Chemical Society, Faraday Transactions. ,vol. 77, pp. 1553- 1562 ,(1981) , 10.1039/F29817701553