Type of Publication: | Journal article |
Publication status: | Published |
Author: | Ji, Lei; Lorbach, Andreas; Edkins, Robert M.; Marder, Todd B. |
Year of publication: | 2015 |
Published in: | The Journal of Organic Chemistry ; 80 (2015), 11. - pp. 5658-5665. - ISSN 0022-3263. - eISSN 1520-6904 |
Pubmed ID: | 25927248 |
DOI (citable link): | https://dx.doi.org/10.1021/acs.joc.5b00618 |
Summary: |
We report a general and selective method to synthesize 2,7-disubstituted pyrene derivatives containing two different substituents by sequential Ir-catalyzed borylation and substitution chemistry. To demonstrate the utility of our approach, we synthesized 2-cyano-7-(N,N-diethylamino)pyrene (3), a pyrene analogue of the widely studied chromophore 4-(N,N-dimethylamino)benzonitrile (DMABN). Compound 3 and the monosubstituted compounds 2-(N,N-diethylamino)pyrene (1) and 2-cyanopyrene (2) have been structurally characterized. Their electronic and optical properties have been studied by a combination of absorption and emission spectroscopies, lifetime and quantum yield measurements, and modeling by DFT and TD-DFT. The photophysical properties of 3 are compared to those of DMABN and 2-cyano-7-(N,N-dimethylamino)-4,5,9,10-tetrahydropyrene, and we show that 2,7-disubstituted pyrene is a moderately effective π-bridge for the construction of donor-acceptor compounds. It is also shown that donor or acceptor groups are only effective at the 2,7-positions of pyrene if they are suitably strong, leading to a switch in the energetic ordering of the HOMO-1 and HOMO or the LUMO and LUMO+1 of pyrene, respectively.
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Subject (DDC): | 540 Chemistry |
Bibliography of Konstanz: | Yes |
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JI, Lei, Andreas LORBACH, Robert M. EDKINS, Todd B. MARDER, 2015. Synthesis and Photophysics of a 2,7-Disubstituted Donor–Acceptor Pyrene Derivative : An Example of the Application of Sequential Ir-Catalyzed C–H Borylation and Substitution Chemistry. In: The Journal of Organic Chemistry. 80(11), pp. 5658-5665. ISSN 0022-3263. eISSN 1520-6904. Available under: doi: 10.1021/acs.joc.5b00618
@article{Ji2015Synth-39228, title={Synthesis and Photophysics of a 2,7-Disubstituted Donor–Acceptor Pyrene Derivative : An Example of the Application of Sequential Ir-Catalyzed C–H Borylation and Substitution Chemistry}, year={2015}, doi={10.1021/acs.joc.5b00618}, number={11}, volume={80}, issn={0022-3263}, journal={The Journal of Organic Chemistry}, pages={5658--5665}, author={Ji, Lei and Lorbach, Andreas and Edkins, Robert M. and Marder, Todd B.} }
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