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Light-Harvesting Crystals Formed from BODIPY-Proline Biohybrid Conjugates: Antenna Effects and Excitonic Coupling
[Image: see text] A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., Φ(F) = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key build...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9097531/ https://www.ncbi.nlm.nih.gov/pubmed/35230124 http://dx.doi.org/10.1021/acs.jpca.2c00035 |
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author | Waly, Sara M. Karlsson, Joshua K. G. Waddell, Paul G. Benniston, Andrew C. Harriman, Anthony |
author_facet | Waly, Sara M. Karlsson, Joshua K. G. Waddell, Paul G. Benniston, Andrew C. Harriman, Anthony |
author_sort | Waly, Sara M. |
collection | PubMed |
description | [Image: see text] A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., Φ(F) = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key building block for the crystal is a pseudo-dimer where hydrogen bonding aligns the proline groups and separates the terminal chromophores by ca. 25 Å. Comparison with a covalently linked bichromophore suggests that one-dimensional (1D) excitonic coupling between the terminals is too small to perturb the optical properties. However, accretion of the pseudo-dimer forms narrow channels possessing a high density of chromophores. The resultant absorption spectrum exhibits strong excitonic splitting, which can be explained quantitatively using the extended dipole approach and allowing for coupling between ca. 30 BODIPY units. Fluorescence, which decays with a lifetime of 2.2 ns, is assigned to a delocalized and (slightly) super-radiant BODIPY dimer situated at the interface and populated via electronic energy transfer from the interior. |
format | Online Article Text |
id | pubmed-9097531 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-90975312022-05-13 Light-Harvesting Crystals Formed from BODIPY-Proline Biohybrid Conjugates: Antenna Effects and Excitonic Coupling Waly, Sara M. Karlsson, Joshua K. G. Waddell, Paul G. Benniston, Andrew C. Harriman, Anthony J Phys Chem A [Image: see text] A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., Φ(F) = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key building block for the crystal is a pseudo-dimer where hydrogen bonding aligns the proline groups and separates the terminal chromophores by ca. 25 Å. Comparison with a covalently linked bichromophore suggests that one-dimensional (1D) excitonic coupling between the terminals is too small to perturb the optical properties. However, accretion of the pseudo-dimer forms narrow channels possessing a high density of chromophores. The resultant absorption spectrum exhibits strong excitonic splitting, which can be explained quantitatively using the extended dipole approach and allowing for coupling between ca. 30 BODIPY units. Fluorescence, which decays with a lifetime of 2.2 ns, is assigned to a delocalized and (slightly) super-radiant BODIPY dimer situated at the interface and populated via electronic energy transfer from the interior. American Chemical Society 2022-03-01 2022-03-10 /pmc/articles/PMC9097531/ /pubmed/35230124 http://dx.doi.org/10.1021/acs.jpca.2c00035 Text en © 2022 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Waly, Sara M. Karlsson, Joshua K. G. Waddell, Paul G. Benniston, Andrew C. Harriman, Anthony Light-Harvesting Crystals Formed from BODIPY-Proline Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title | Light-Harvesting Crystals Formed from BODIPY-Proline
Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title_full | Light-Harvesting Crystals Formed from BODIPY-Proline
Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title_fullStr | Light-Harvesting Crystals Formed from BODIPY-Proline
Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title_full_unstemmed | Light-Harvesting Crystals Formed from BODIPY-Proline
Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title_short | Light-Harvesting Crystals Formed from BODIPY-Proline
Biohybrid Conjugates: Antenna Effects and Excitonic Coupling |
title_sort | light-harvesting crystals formed from bodipy-proline
biohybrid conjugates: antenna effects and excitonic coupling |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9097531/ https://www.ncbi.nlm.nih.gov/pubmed/35230124 http://dx.doi.org/10.1021/acs.jpca.2c00035 |
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