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

Photochemical & Photobiological Sciences Pub Date: 2003-02-12 DOI: 10.1039/B211838F

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.

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