| 1. |
- Gorski, Krzysztof, et al.
(författare)
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Quadrupolar Dyes Based on Highly Polarized Coumarins
- 2021
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Ingår i: Organic Letters. - : AMER CHEMICAL SOC. - 1523-7060 .- 1523-7052. ; 23:17, s. 6770-6774
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Tidskriftsartikel (refereegranskat)abstract
- The fluorescence and other photophysical parameters of highly polarized, quadrupolar bis-coumarins possessing an electron-rich pyrrolo[3,2-b]pyrrole bridging unit are highly dependent on the linking position between both chromophores. Delocalization of the LUMO on the entire pi-system results in intense emission and strong two-photon absorption.
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| 2. |
- Gorski, Krzysztof, et al.
(författare)
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The interplay of intersystem crossing and internal conversion in quadrupolar tetraarylpyrrolo[3,2-b]pyrroles
- 2024
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Ingår i: Journal of Materials Chemistry C. - : ROYAL SOC CHEMISTRY. - 2050-7526 .- 2050-7534.
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Tidskriftsartikel (refereegranskat)abstract
- Adding nitro groups to aromatic compounds usually quenches their fluorescence via intersystem crossing (ISC) or internal conversion (IC). Herein, we investigated centrosymmetric 1,4-dihydropyrrolo[3,2-b]pyrroles linked to variously substituted nitro-heteroaryls. A 1,4-orientation of the nitro substituent versus the electron rich 1,4-dihydropyrrolo[3,2-b]pyrrole core invokes a strong fluorescence in non-polar solvents and intense two-photon absorption while a 1,3-orientation of push-pull substituents results in a dramatic hypsochromic shift of absorption, weak, bathochromically shifted emission and weak two-photon absorption. The combined experimental and computational study indicates that the primary responsible factors are: (1) the difference in electron density distribution in the LUMO; (2) the difference in mu 10. IC is a dominant mechanism of non-radiative dissipation of energy in all these dyes but as long as the distribution of electron density within the HOMO and LUMO is delocalized on the 1,4-dihydropyrrolo[3,2-b]pyrrole core as well as on the nitroaromatic moieties its rate is slower than the fluorescence rate in non-polar solvents.
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| 3. |
- Poronik, Yevgen M., et al.
(författare)
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Deciphering the unusual fluorescence in weakly coupled bis-nitro-pyrrolo[3,2-b]pyrroles
- 2020
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Ingår i: Communications Chemistry. - : NATURE RESEARCH. - 2399-3669. ; 3:1
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Tidskriftsartikel (refereegranskat)abstract
- Electron-deficient pi-conjugated functional dyes lie at the heart of organic optoelectronics. Adding nitro groups to aromatic compounds usually quenches their fluorescence via inter-system crossing (ISC) or internal conversion (IC). While strong electronic coupling of the nitro groups with the dyes ensures the benefits from these electron-withdrawing substituents, it also leads to fluorescence quenching. Here, we demonstrate how such electronic coupling affects the photophysics of acceptor-donor-acceptor fluorescent dyes, with nitrophenyl acceptors and a pyrrolo[3,2-b]pyrrole donor. The position of the nitro groups and the donor-acceptor distance strongly affect the fluorescence properties of the bis-nitrotetraphenylpyrrolopyrroles. Concurrently, increasing solvent polarity quenches the emission that recovers upon solidifying the media. Intramolecular charge transfer (CT) and molecular dynamics, therefore, govern the fluorescence of these nitro-aromatics. While balanced donor-acceptor coupling ensures fast radiative deactivation and slow ISC essential for large fluorescence quantum yields, vibronic borrowing accounts for medium dependent IC via back CT. These mechanistic paradigms set important design principles for molecular photonics and electronics. Owing to their electron-withdrawing nature, nitro-groups are desirable in the design of electron-deficient light-sensitizing aromatic pi-conjugated molecules, but most nitro-aromatics are not fluorescent. Here, the authors show how balanced donor-acceptor coupling ensures fast radiative deactivation and slow intersystem crossing in bis-nitrotetraphenylpyrrolopyrroles.
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| 4. |
- Szymanski, Bartosz, et al.
(författare)
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The effect of rigidity on the emission of quadrupolar strongly polarized dyes
- 2024
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Ingår i: New Journal of Chemistry. - : ROYAL SOC CHEMISTRY. - 1144-0546 .- 1369-9261.
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Tidskriftsartikel (refereegranskat)abstract
- Hybrid dyes comprising 1,4-dihydropyrrolo[3,2-b]pyrrole and two strongly electron-withdrawing benzoxadiazole substituents, differing in their level of planarization, offer an insightful window into the interplay between internal conversion and intersystem crossing as relaxation pathways from the excited state. The emission intensity is strong for non-fused systems whilst it is minimal for fused dyes. Computational evaluation has revealed that internal conversion, and not inter-system crossing, is the main non-radiative process for planar, fused quadrupolar dyes. Planarization of the pyrrolopyrrole chromophore switches the mechanism of non-radiative deactivation from intersystem crossing to internal conversion.
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| 5. |
- Weclawski, Marek K., et al.
(författare)
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Biscoumarin-containing acenes as stable organic semiconductors for photocatalytic oxygen reduction to hydrogen peroxide
- 2017
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Ingår i: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488. ; 5:39, s. 20780-20788
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Tidskriftsartikel (refereegranskat)abstract
- Conversion of solar energy into chemical energy in the form of hydrogen peroxide and other reactive oxygen species has been predicted to be an efficient strategy, yet few organic materials systems support these types of photochemical conversion reactions. Herein we report a simple synthetic route to yield biscoumarin-containing acenes, semiconducting small molecules with exceptional stability and tunable electrochemical and electrical properties. We find that these semiconductors are photo(electro) catalysts capable of reducing oxygen to hydrogen peroxide. Visible light irradiation of thin films on insulating substrates in pure water results in H2O2 photogeneration with water as the sacrificial electron donor. Thin films on conducting substrates are robust catalytic photocathodes for producing H2O2. These semiconductor photoelectrodes retain their catalytic properties in a pH range from 2-13. Photocatalytic or photoelectrocatalytic deployment of biscoumarin-containing acenes does not lead to measurable degradation. This work demonstrates a strategy to synthesize stable organic semiconductors not only suitable for thin-film electronic devices but also next-generation photocatalytic concepts.
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