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

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

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JIN, 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. 144(30), pp. 13704-13716. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/jacs.2c04516

@article{Jin2022-08-03Explo-58340, title={Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory}, year={2022}, doi={10.1021/jacs.2c04516}, 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} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/58340"> <dc:creator>Mewes, Jan-Michael</dc:creator> <dc:creator>Braun, Markus</dc:creator> <dcterms:title>Exploring Structure-Property Relations of B,S-Doped Polycyclic Aromatic Hydrocarbons through the Trinity of Synthesis, Spectroscopy, and Theory</dcterms:title> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/58340"/> <dc:creator>Winter, Rainer F.</dc:creator> <dc:contributor>Jin, Tao</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2022-08-19T08:57:49Z</dc:date> <dc:contributor>Breimaier, Stefanie</dc:contributor> <dc:contributor>Lerner, Hans-Wolfram</dc:contributor> <dc:creator>Jin, Tao</dc:creator> <dc:creator>Kunze, Lukas</dc:creator> <dc:contributor>Kunze, Lukas</dc:contributor> <dc:contributor>Braun, Markus</dc:contributor> <dc:creator>Wagner, Matthias</dc:creator> <dcterms:abstract xml:lang="eng">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.</dcterms:abstract> <dc:language>eng</dc:language> <dcterms:issued>2022-08-03</dcterms:issued> <dc:creator>Jäkle, Frieder</dc:creator> <dc:contributor>Jäkle, Frieder</dc:contributor> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:contributor>Bolte, Michael</dc:contributor> <dc:creator>Bolte, Michael</dc:creator> <dc:creator>Lerner, Hans-Wolfram</dc:creator> <dc:contributor>Mewes, Jan-Michael</dc:contributor> <dc:contributor>Winter, Rainer F.</dc:contributor> <dc:contributor>Wagner, Matthias</dc:contributor> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:creator>Breimaier, Stefanie</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2022-08-19T08:57:49Z</dcterms:available> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> </rdf:Description> </rdf:RDF>

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