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Boron-Doped Tri(9,10-anthrylene)s: Synthesis, Structural Characterization, and Optoelectronic Properties

Authors

  • Dipl.-Chem. Claas Hoffend,

    1. Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
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  • Frauke Schödel,

    1. Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
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  • Dr. Michael Bolte,

    1. Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
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  • Dr. Hans-Wolfram Lerner,

    1. Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
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  • Prof. Dr. Matthias Wagner

    Corresponding author
    1. Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
    • Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main (Germany), Fax: (+49) 69-798-29260
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Abstract

The reaction of 9,10-dibromo-9,10-dihydro-9,10-diboraanthracene (9,10-dibromo-DBA, 3) with two equivalents of 9-lithio-2,6- or 9-lithio-2,7-di-tert-butylanthracene gave the corresponding 9,10-dianthryl-DBAs featuring two (4) or four (5) inward-pointing tert-butyl groups. Compound 4 exists as two atropisomers, 4 and 4′, due to hindered rotation about the exocyclic B[BOND]C bonds. X-ray crystallography of 5 suggests that the overall interactions between facing tert-butyl groups are attractive rather than repulsive. Even in solution, 4/4′ and 5 are stable toward air and moisture for several hours. Treatment of 3 with 10-lithio-9-R-2,7-di-tert-butylanthracenes carrying phenyl (R=Ph), dimesitylboryl (R=Mes2B), or N,N-di(p-tolyl)amino (R=Tol2N) groups gave the corresponding 9,10-dianthryl-DBA derivatives 911 in moderate to good yields. In these molecules, all four solubilizing tert-butyl groups are outward pointing. The solid-state structures of 4, 5, 9, and 10 reveal twisted conformations about the exocyclic B[BOND]C bonds with dihedral angles of 70–90°. A significant electron-withdrawing character was proven for the Mes2B moiety, but no appreciable +M effect was evident for Tol2N. Compounds 5, 9, and 11 show two reversible DBA-centered reduction waves in the cyclic voltammogram. In the case of 10, a third reversible redox transition can be assigned to the Mes2B–anthryl substituents. The UV/Vis absorption spectrum of 5 is characterized by a very broad band at λmax=510 nm, attributable to a twisted intramolecular charge-transfer interaction from the anthryl donors to the DBA acceptor. The corresponding emission band shows pronounced positive solvatochromism (λem=567 nm, C6H12; 680 nm, CH2Cl2) in line with a highly polar excited state. The charge-transfer bands of 10 and 11, as well as the emission bands of 9 and 10, are redshifted relative to those of 5. The Tol2N derivative 11 is essentially nonfluorescent in solution, but emits bright wine-red light in the solid state.

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