Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory

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2022
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Jin, Tao
Kunze, Lukas
Bolte, Michael
Lerner, Hans-Wolfram
Jäkle, Frieder
Braun, Markus
Mewes, Jan-Michael
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Journal of the American Chemical Society. American Chemical Society. 2022, 144(30), pp. 13704-13716. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/jacs.2c04516
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Polycyclic aromatic hydrocarbons (PAHs) are prominent lead structures for organic optoelectronic materials. This work describes the synthesis of three B,S-doped PAHs with heptacene-type scaffolds via nucleophilic aromatic substitution reactions between fluorinated arylborane precursors and 1,2-(Me3SiS)2C6H4/1,8-diazabicyclo[5.4.0]undec-7-ene (72-92% yield). All compounds contain tricoordinate B atoms at their 7,16-positions, kinetically protected by mesityl (Mes) substituents. PAHs 1/2 feature two/four S atoms at their 5,18-/5,9,14,18-positions; PAH 3 is a 6,8,15,17-tetrafluoro derivative of 2. For comparison, we also prepared the skewed naphtho[2,3-c]pentaphene-type isomer 4. The simultaneous presence of electron-accepting B atoms and electron-donating S atoms results in a redox-ambiphilic behavior; the radical cations [1•]+ and [2•]+ were characterized by electron paramagnetic resonance spectroscopy. Several low-lying charge-transfer states exist, some of which (especially S-to-B and Mes-to-B transitions) compete on the excited-state potential-energy surface. Consistent with the calculated state characters and oscillator strengths, this competition results in a spread of fluorescence quantum yields (2-27%). The optoelectronic properties of 1 change drastically upon addition of Ag+ ions: while the color of 1 in CH2Cl2 changes bathochromically from yellow to red (λmax from 463 to 486 nm; -0.13 eV), the emission band shifts hypsochromically from 606 to 545 nm (+0.23 eV), and the fluorescence quantum yield increases from 12 to 43%. According to titration experiments, higher order adducts [Agn1m]n+ are formed. As a suitable system for modeling Ag+ complexation, our calculations predict a dimer structure (n = m = 2) with Ag2S4 core, approximately linear S-Ag-S fragments, and Ag-Ag interaction. The computed optoelectronic properties of [Ag212]2+ agree well with the experimentally observed ones.

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ISO 690JIN, Tao, Lukas KUNZE, Stefanie BREIMAIER, Michael BOLTE, Hans-Wolfram LERNER, Frieder JÄKLE, Rainer F. WINTER, Markus BRAUN, Jan-Michael MEWES, Matthias WAGNER, 2022. Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory. In: Journal of the American Chemical Society. American Chemical Society. 2022, 144(30), pp. 13704-13716. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/jacs.2c04516
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@article{Jin2022-08-03Explo-58340,
  year={2022},
  doi={10.1021/jacs.2c04516},
  title={Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory},
  number={30},
  volume={144},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={13704--13716},
  author={Jin, Tao and Kunze, Lukas and Breimaier, Stefanie and Bolte, Michael and Lerner, Hans-Wolfram and Jäkle, Frieder and Winter, Rainer F. and Braun, Markus and Mewes, Jan-Michael and Wagner, Matthias}
}
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