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Studies of the solvatochromic emission properties of N-aroylurea derivatives II: influence of hydrogen-bonding interactions

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Abstract

The solvatochromic emission properties of five naphthoylurea derivatives with different substitution patterns at the naphthoylurea functionality were investigated, with a particular focus on the influence of inter- and intramolecular H-bonding interactions. The bathochromic shifts of the emission maxima correlate well with the acceptor number or Catalán’s acidity of the solvent (Δλ = 47–86 nm), indicating an excited species with a pronounced negative charge that is stabilized by H-bond donating (HBD) solvents. In media with restricted free volume the formation of the charged species is not favored, because the required conformational change to establish an intramolecular charge transfer (ICT) between the fluorophore and the acylurea substituent is hindered, and the emission mainly originates from the locally excited state. This relationship between the alignment of the naphthoyl carbonyl functionality relative to the naphthyl ring and the spectroscopic shift was confirmed by the comparison of the ground state conformation and the emission spectra of the naphthoylurea derivatives in the solid state. Time-resolved experiments revealed different excited entities, whose lifetimes are significantly influenced by the HBD properties and the temperature of the environment. With few exceptions the naphthoylurea derivatives exhibit only two emissive species in the nanosecond range. All experimental data point to conformational relaxation and solvent reorganization leading to the cis and trans isomers of one preferential conformer with respect to the acylurea unit. The structure of the preferred conformation is mainly determined by the possible inter- or intramolecular H-bonds and is therefore also strongly influenced by the HBD and H-bond accepting (HBA) properties of the polar solvents. As the NH groups of the acylurea functionality contribute mainly to the entire inter- and intramolecular H-bond arrangement the variation of the substitution pattern of the urea unit, specifically the presence and position of the NH groups, leads to derivatives with significantly different steady-state and time-resolved emission properties.

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Authors and Affiliations

  1. Department of Chemistry and Biology, University of Siegen, Adolf-Reichwein-Str. 2, D-57068, Siegen, Germany

    Anna Bergen, Heiko Ihmels, Hans-Jörg Deiseroth & Elmar Neumann

  2. Department of Chemistry, University of Victoria, PO Box 3065, Victoria, BC, Canada, V8W 3V6

    Cornelia Bohne & Denis Fuentealba

  3. Institute of Organic Chemistry and Chemical Biology, University of Frankfurt, Max von Laue Strasse 7, D-60438, Frankfurt am Main, Germany

    Jan Willem Bats

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  1. Anna Bergen
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Correspondence to Cornelia Bohne or Heiko Ihmels.

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Electronic supplementary information (ESI) available: 1H-NMR spectroscopy and X-ray diffraction analysis; absorption and steady-state emission properties in different solvents; time-resolved emission properties in different solvents; studies in media with different viscosity and temperature; 1H-NMR and 13C-NMR data of 2a–e. CCDC 884407 (2a), 880988 (2b), 880989 (2c) and 884408 (2d). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2pp25167a

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Bergen, A., Bohne, C., Fuentealba, D. et al. Studies of the solvatochromic emission properties of N-aroylurea derivatives II: influence of hydrogen-bonding interactions. Photochem Photobiol Sci 11, 1914–1928 (2012). https://doi.org/10.1039/c2pp25167a

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