Structural concept for fluorinated Y-enynes with solvatochromic properties

  • An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert–Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formaAn approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert–Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 °C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7–9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene–arene, and fluorine–π interactions.show moreshow less

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Metadaten
Author:Bilal R. Kaafarani, Brigitte Wex, Bernd Strehmel, Douglas C. Neckers
URN:urn:nbn:de:kobv:517-opus-13168
Series (Serial Number):Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe (paper 027)
Document Type:Postprint
Language:English
Date of Publication (online):2007/04/25
Year of Completion:2002
Publishing Institution:Universität Potsdam
Release Date:2007/04/25
Source:Photochemical and Photobiological Sciences. - ISSN 1474-905X. - 1 (2002), p. 942-950
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Extern / Extern
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Collections:Universität Potsdam / Aufsätze (Pre- und Postprints) / Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie / Physikalische Chemie
Notes extern:
first published in:
Photochemical and Photobiological Sciences : an international journal ; the official journal of the European Photochemistry Association and the European Society for Photobiology. - ISSN 1474-905X. - 1 (2002), S. 942-950
doi: 10.1039/b208326d
Reproduced by permission of The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology and the European Photochemistry Association