3,9-Disubstituted Bis[1]benzothieno[3,2-b;2',3'-e][1,4]thiazines with Low Oxidation Potentials and Enhanced Emission
Dibrominated bis[1]benzothieno[3,2-b;2',3'-e][1,4]thiazines (BBTT) are efficiently synthesized and applied in Suzuki and Buchwald-Hartwig cross-coupling reactions to give access to 3,9-disubstituted BBTT derivatives with extended π-conjugation and enhanced electronic properties. For instance, 3,9-di(hetero)aryl substituted BBTT derivatives surpass their parent congeners phenothiazines with lower oxidation potentials and pronounced yellow to orange-red fluorescence (Φf ≈ 30-45%). In addition, 3,9-bis(di(hetero)arylamino substituted BBTT possess very high lying HOMO energy (EHOMO = -4.46 to -4.83 eV), a favorable property of hole transport molecules. A representative X-ray structure analysis reveals that the central BBTT core in these extended π-systems is essentially planarized. Upon protonation of a 3,9-bis(di(hetero)arylamino) substituted BBTT, the absorption color shifts from yellow to deep blue with a concomitant loss of the emission. The optical properties of these novel BBTT derivatives can be plausibly rationalized by time-dependent density functional theory (TD(DFT)) calculations and correlation between experimentally determined oxidation potentials and σp parameters as well as between photophysical data and the specific substituent parameter σp- by establishing electronic structure-property relationships.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2021 |
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| Erschienen: |
2021 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:86 |
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| Enthalten in: |
The Journal of organic chemistry - 86(2021), 12 vom: 18. Juni, Seite 8000-8014 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Berens, Henning R V [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 18.06.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.joc.1c00397 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM326495614 |
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| 245 | 1 | 0 | |a 3,9-Disubstituted Bis[1]benzothieno[3,2-b;2',3'-e][1,4]thiazines with Low Oxidation Potentials and Enhanced Emission |
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| 500 | |a Date Revised 18.06.2021 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Dibrominated bis[1]benzothieno[3,2-b;2',3'-e][1,4]thiazines (BBTT) are efficiently synthesized and applied in Suzuki and Buchwald-Hartwig cross-coupling reactions to give access to 3,9-disubstituted BBTT derivatives with extended π-conjugation and enhanced electronic properties. For instance, 3,9-di(hetero)aryl substituted BBTT derivatives surpass their parent congeners phenothiazines with lower oxidation potentials and pronounced yellow to orange-red fluorescence (Φf ≈ 30-45%). In addition, 3,9-bis(di(hetero)arylamino substituted BBTT possess very high lying HOMO energy (EHOMO = -4.46 to -4.83 eV), a favorable property of hole transport molecules. A representative X-ray structure analysis reveals that the central BBTT core in these extended π-systems is essentially planarized. Upon protonation of a 3,9-bis(di(hetero)arylamino) substituted BBTT, the absorption color shifts from yellow to deep blue with a concomitant loss of the emission. The optical properties of these novel BBTT derivatives can be plausibly rationalized by time-dependent density functional theory (TD(DFT)) calculations and correlation between experimentally determined oxidation potentials and σp parameters as well as between photophysical data and the specific substituent parameter σp- by establishing electronic structure-property relationships | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Mohammad, Kausar |e verfasserin |4 aut | |
| 700 | 1 | |a Reiss, Guido J |e verfasserin |4 aut | |
| 700 | 1 | |a Müller, Thomas J J |e verfasserin |4 aut | |
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