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Singlet excited state dipole moments of dual fluorescent N-phenylpyrroles and 4-(dimethylamino)benzonitrile from solvatochromic and thermochromic spectral shifts

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Abstract

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.

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Author notes

  1. Toshitada Yoshihara

    Present address: Present address: National Institute of Advanced Industrial Science and Technology (AIST), Photoreaction Control Research Center, Higashi 1-1-1, Tsukuba, Ibaragi, 305-8565, Japan

  2. Satyen Saha

    Present address: Present address: School of Chemistry, University of Hyderabad, Hyderabad, 500 046, India

Authors and Affiliations

  1. Spektroskopie und Photochemische Kinetik, Max-Planck-Institut für biophysikalische Chemie, 37070, Göttingen, Germany

    Toshitada Yoshihara, Victor A. Galievsky, Sergey I. Druzhinin, Satyen Saha & Klaas A. Zachariasse

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  1. Toshitada Yoshihara
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  2. Victor A. Galievsky
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Correspondence to Klaas A. Zachariasse.

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Dedicated to Professor Jean Kossanyi on the occasion of his 70th birthday.

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Yoshihara, T., Galievsky, V.A., Druzhinin, S.I. et al. Singlet excited state dipole moments of dual fluorescent N-phenylpyrroles and 4-(dimethylamino)benzonitrile from solvatochromic and thermochromic spectral shifts. Photochem Photobiol Sci 2, 342–353 (2003). https://doi.org/10.1039/b211838f

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