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Intramolecular Charge Transfer and Ultrafast Nonradiative Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted Squaraines
[Image: see text] Molecular (dye) aggregates are a materials platform of interest in light harvesting, organic optoelectronics, and nanoscale computing, including quantum information science (QIS). Strong excitonic interactions between dyes are key to their use in QIS; critically, properties of the...
Autores principales: | , , , , , , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9923757/ https://www.ncbi.nlm.nih.gov/pubmed/36705555 http://dx.doi.org/10.1021/acs.jpca.2c06442 |
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author | Wright, Nicholas D. Huff, Jonathan S. Barclay, Matthew S. Wilson, Christopher K. Barcenas, German Duncan, Katelyn M. Ketteridge, Maia Obukhova, Olena M. Krivoshey, Alexander I. Tatarets, Anatoliy L. Terpetschnig, Ewald A. Dean, Jacob C. Knowlton, William B. Yurke, Bernard Li, Lan Mass, Olga A. Davis, Paul H. Lee, Jeunghoon Turner, Daniel B. Pensack, Ryan D. |
author_facet | Wright, Nicholas D. Huff, Jonathan S. Barclay, Matthew S. Wilson, Christopher K. Barcenas, German Duncan, Katelyn M. Ketteridge, Maia Obukhova, Olena M. Krivoshey, Alexander I. Tatarets, Anatoliy L. Terpetschnig, Ewald A. Dean, Jacob C. Knowlton, William B. Yurke, Bernard Li, Lan Mass, Olga A. Davis, Paul H. Lee, Jeunghoon Turner, Daniel B. Pensack, Ryan D. |
author_sort | Wright, Nicholas D. |
collection | PubMed |
description | [Image: see text] Molecular (dye) aggregates are a materials platform of interest in light harvesting, organic optoelectronics, and nanoscale computing, including quantum information science (QIS). Strong excitonic interactions between dyes are key to their use in QIS; critically, properties of the individual dyes govern the extent of these interactions. In this work, the electronic structure and excited-state dynamics of a series of indolenine-based squaraine dyes incorporating dimethylamino (electron donating) and/or nitro (electron withdrawing) substituents, so-called asymmetric dyes, were characterized. The dyes were covalently tethered to DNA Holliday junctions to suppress aggregation and permit characterization of their monomer photophysics. A combination of density functional theory and steady-state absorption spectroscopy shows that the difference static dipole moment (Δd) successively increases with the addition of these substituents while simultaneously maintaining a large transition dipole moment (μ). Steady-state fluorescence and time-resolved absorption and fluorescence spectroscopies uncover a significant nonradiative decay pathway in the asymmetrically substituted dyes that drastically reduces their excited-state lifetime (τ). This work indicates that Δd can indeed be increased by functionalizing dyes with electron donating and withdrawing substituents and that, in certain classes of dyes such as these asymmetric squaraines, strategies may be needed to ensure long τ, e.g., by rigidifying the π-conjugated network. |
format | Online Article Text |
id | pubmed-9923757 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-99237572023-02-14 Intramolecular Charge Transfer and Ultrafast Nonradiative Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted Squaraines Wright, Nicholas D. Huff, Jonathan S. Barclay, Matthew S. Wilson, Christopher K. Barcenas, German Duncan, Katelyn M. Ketteridge, Maia Obukhova, Olena M. Krivoshey, Alexander I. Tatarets, Anatoliy L. Terpetschnig, Ewald A. Dean, Jacob C. Knowlton, William B. Yurke, Bernard Li, Lan Mass, Olga A. Davis, Paul H. Lee, Jeunghoon Turner, Daniel B. Pensack, Ryan D. J Phys Chem A [Image: see text] Molecular (dye) aggregates are a materials platform of interest in light harvesting, organic optoelectronics, and nanoscale computing, including quantum information science (QIS). Strong excitonic interactions between dyes are key to their use in QIS; critically, properties of the individual dyes govern the extent of these interactions. In this work, the electronic structure and excited-state dynamics of a series of indolenine-based squaraine dyes incorporating dimethylamino (electron donating) and/or nitro (electron withdrawing) substituents, so-called asymmetric dyes, were characterized. The dyes were covalently tethered to DNA Holliday junctions to suppress aggregation and permit characterization of their monomer photophysics. A combination of density functional theory and steady-state absorption spectroscopy shows that the difference static dipole moment (Δd) successively increases with the addition of these substituents while simultaneously maintaining a large transition dipole moment (μ). Steady-state fluorescence and time-resolved absorption and fluorescence spectroscopies uncover a significant nonradiative decay pathway in the asymmetrically substituted dyes that drastically reduces their excited-state lifetime (τ). This work indicates that Δd can indeed be increased by functionalizing dyes with electron donating and withdrawing substituents and that, in certain classes of dyes such as these asymmetric squaraines, strategies may be needed to ensure long τ, e.g., by rigidifying the π-conjugated network. American Chemical Society 2023-01-27 /pmc/articles/PMC9923757/ /pubmed/36705555 http://dx.doi.org/10.1021/acs.jpca.2c06442 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Wright, Nicholas D. Huff, Jonathan S. Barclay, Matthew S. Wilson, Christopher K. Barcenas, German Duncan, Katelyn M. Ketteridge, Maia Obukhova, Olena M. Krivoshey, Alexander I. Tatarets, Anatoliy L. Terpetschnig, Ewald A. Dean, Jacob C. Knowlton, William B. Yurke, Bernard Li, Lan Mass, Olga A. Davis, Paul H. Lee, Jeunghoon Turner, Daniel B. Pensack, Ryan D. Intramolecular Charge Transfer and Ultrafast Nonradiative Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted Squaraines |
title | Intramolecular
Charge Transfer and Ultrafast Nonradiative
Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted
Squaraines |
title_full | Intramolecular
Charge Transfer and Ultrafast Nonradiative
Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted
Squaraines |
title_fullStr | Intramolecular
Charge Transfer and Ultrafast Nonradiative
Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted
Squaraines |
title_full_unstemmed | Intramolecular
Charge Transfer and Ultrafast Nonradiative
Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted
Squaraines |
title_short | Intramolecular
Charge Transfer and Ultrafast Nonradiative
Decay in DNA-Tethered Asymmetric Nitro- and Dimethylamino-Substituted
Squaraines |
title_sort | intramolecular
charge transfer and ultrafast nonradiative
decay in dna-tethered asymmetric nitro- and dimethylamino-substituted
squaraines |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9923757/ https://www.ncbi.nlm.nih.gov/pubmed/36705555 http://dx.doi.org/10.1021/acs.jpca.2c06442 |
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